Hierarchical structure is a key feature explaining the superior properties of many materials in nature. Fibers usually serve in textiles, for structural reinforcement, or as support for other materials, whereas spherical micro- and nanoobjects can be either highly functional or also used as fillers to reinforce structure materials. Combining nanocontainers with fibers in one single object has been used to increase the functionality of fibers, for example, antibacterial and thermoregulation, when the advantageous properties given by the encapsulated materials inside the containers are transferred to the fibers. Herein we focus our discussion on how the hierarchical structure composed of nanocontainers in nanofibers yields materials displaying advantages of both types of materials and sometimes synergetical effects. Such materials can be produced by first carefully designing nanocontainers with defined morphology and chemistry and subsequently electrospinning them to fabricate nanofibers. This method, called colloid-electrospinning, allows for marrying the properties of nanocontainers and nanofibers. The obtained fibers could be successfully applied in different fields such as catalysis, optics, energy conversion and production, and biomedicine. The miniemulsion process is a convenient approach for the encapsulation of hydrophobic or hydrophilic payloads in nanocontainers. These nanocontainers can be embedded in fibers by the colloid-electrospinning technique. The combination of nanocontainers with nanofibers by colloid-electrospinning has several advantages. (1) The fiber matrix serves as support for the embedded nanocontainers. For example, through combining catalysts nanoparticles with fiber networks, the catalysts can be easily separated from the reaction media and handled visually. This combination is beneficial for the reuse of the catalyst and the purification of products. (2) Electrospun nanofibers containing nanocontainers offer the active agents inside the nanocontainers a double protection by both the fiber matrix and the nanocontainers. Since the polymer of the fibers and the polymer of the nanocontainers have usually opposite polarities, the encapsulated substance, for example, catalysts, dyes, or drugs, can be protected against a large variety of environmental influences. (3) Electrospun nanofibers exhibit unique advantages for tissue engineering and drug delivery that are a structural similarity to the extracellular matrix of biological tissues, large specific surface area, high and interconnected porosity which enhances cell adhesion, proliferation, drug loading, and mass transfer properties, as well as the flexibility in selecting the raw materials. Moreover, the nanocontainer-in-nanofiber structure allows multidrug loading and programmable release of each drug, which are very important to achieve synergistic effects in tissue engineering and disease therapy. The advantages offered by these materials encourage us to further understand the relationship between colloidal properties and fibers, to pre...