Cartilage replacement materials exhibiting a set of demanding properties such as high water content, high mechanical stiffness, low friction, and excellent biocompatibility are quite difficult to achieve. Here, poly(p‐phenylene‐2,6‐benzobisoxazole) (PBO) nanofibers are combined with polyvinyl alcohol (PVA) to form a super‐strong structure with a performance that surpasses the vast majority of previously existing hydrogels. PVA–PBO composites with water contents in the 59–76% range exhibit tensile and compressive moduli reaching 20.3 and 4.5 MPa, respectively, and a coefficient of friction below 0.08. Further, they are biocompatible and support the viability of chondrocytes for 1 week, with significant improvements in cell adhesion, proliferation, and differentiation compared to PVA. The new composites can be safely sterilized by steam heat or gamma radiation without compromising their integrity and overall performance. In addition, they show potential to be used as local delivery platforms for anti‐inflammatory drugs. These attractive features make PVA–PBO composites highly competitive engineered materials with remarkable potential for use in the design of load‐bearing tissues. Complementary work has also revealed that these composites will be interesting alternatives in other industrial fields where high thermal and mechanical resistance are essential requirements, or which can take advantage of the pH responsiveness functionality.