A comprehensive review on the five levels of hierarchical structures of silk materials and the correlation with macroscopic properties/performance of the silk materials, that is, the toughness, strain‐stiffening, etc., is presented. It follows that the crystalline binding force turns out to be very important in the stabilization of silk materials, while the β‐crystallite networks or nanofibrils and the interactions among helical nanofibrils are two of the most essential structural elements, which to a large extent determine the macroscopic performance of various forms of silk materials. In this context, the characteristic structural factors such as the orientation, size, and density of β‐crystallites are very crucial. It is revealed that the formation of these structural elements is mainly controlled by the intermolecular nucleation of β‐crystallites. Consequently, the rational design and reconstruction of silk materials can be implemented by controlling the molecular nucleation via applying sheering force and seeding (i.e., with carbon nanotubes). In general, the knowledge of the correlation between hierarchical structures and performance provides an understanding of the structural reasons behind the fascinating behaviors of silk materials.

Textile-based electronic techniques that can in real-time and noncontact detect the respiration rate and respiratory arrest are highly desired for human health monitoring. Yarn-shaped humidity sensor is fabricated based on a sensitive fiber with relatively high specific surface area and abnormal cross-section. The response and recovery time of the yarnshaped humidity sensor is only 3.5 and 4 s, respectively, with little hysteresis, because of the hydrophobic property of these functional fibers and the grooves on the surface of the fibers, which is much faster than those of the commercial polyimide materials. Moreover, a batteryfree LC wireless testing system combined with the yarn-shaped sensor is fabricated, which is further successfully imbedded into the intelligent mask to detect human breath. Based on the detection of LC wireless testing system, the frequency of 50.25 MHz under the exhaled condition shifts to 50.86 MHz under the inhaled situation of humidity sensor. In essence, the functional yarns with proper structure, would be an excellent candidature to the yarn-shaped humidity sensor, in which there are good performance and wide application possibilities, eventually offering a facile method for the wireless detection of human physiological signals in the field of electronic fabrics.

Textile-based triboelectric nanogenerators (TENG) that can effectively harvest biomechanical energy and sense multifunctional posture and movement have a wide range of applications in next-generation wearable and portable electronic devices. Hence, bulk production of fine yarns with high triboelectric output through a continuous manufacturing process is an urgent task. Here, an ultralight single-electrode triboelectric yarn (SETY) with helical hybridized nano-micro core–shell fiber bundles is fabricated by a facile and continuous electrospinning technology. The obtained SETY device exhibits ultralightness (0.33 mg cm–1), extra softness, and smaller size (350.66 μm in diameter) compared to those fabricated by conventional fabrication techniques. Based on such a textile-based TENG, high energy-harvesting performance (40.8 V, 0.705 μA cm–2, and 9.513 nC cm–2) was achieved by applying a 2.5 Hz mechanical drive of 5 N. Importantly, the triboelectric yarns can identify textile materials according to their different electron affinity energies. In addition, the triboelectric yarns are compatible with traditional textile technology and can be woven into a high-density plain fabric for harvesting biomechanical energy and are also competent for monitoring tiny signals from humans or insects.

Fire disaster is one of the most common hazards that threaten public safety and social development: how to improve the fire escape and rescue capacity remains a huge challenge. Here, a 3D honeycomb‐structured woven fabric triboelectric nanogenerator (F‐TENG) based on a flame‐retardant wrapping yarn is developed. The wrapping yarn is fabricated through a continuous hollow spindle fancy twister technology, which is compatible with traditional textile production processes. The resulting 3D F‐TENG can be used in smart carpets as a self‐powered escape and rescue system that can precisely locate the survivor position and point out the escape route to timely assist victim search and rescuing. As interior decoration, the unique design of the honeycomb weaving structure endows the F‐TENG fabric with an excellent noise‐reduction ability. In addition, combining with its good machine washability, air permeability, flame‐retardency, durability, and repeatability features, the 3D F‐TENG may have great potential applications in fire rescue and wearable sensors as well as smart home decoration.

Turning insulating silk fibroin materials into conductive ones turns out to be the essential step toward achieving active silk flexible electronics. This work aims to acquire electrically conductive biocompatible fibers of regenerated Bombyx mori silk fibroin (SF) materials based on carbon nanotubes (CNTs) templated nucleation reconstruction of silk fibroin networks. The electronical conductivity of the reconstructed mesoscopic functional fibers can be tuned by the density of the incorporated CNTs. It follows that the hybrid fibers experience an abrupt increase in conductivity when exceeding the percolation threshold of CNTs >35 wt%, which leads to the highest conductivity of 638.9 S m−1 among organic‐carbon‐based hybrid fibers, and 8 times higher than the best available materials of the similar types. In addition, the silk‐CNT mesoscopic hybrid materials achieve some new functionalities, i.e., humidity‐responsive conductivity, which is attributed to the coupling of the humidity inducing cyclic contraction of SFs and the conductivity of CNTs. The silk‐CNT materials, as a type of biocompatible electronic functional fibrous material for pressure and electric response humidity sensing, are further fabricated into a smart facial mask to implement respiration condition monitoring for remote diagnosis and medication.