Articular cartilage (AC) degradation is a recurrent pathology that affects millions of people worldwide. Polyvinyl alcohol (PVA) hydrogels have been widely explored for AC replacement. However, their mechanical performance is generally inadequate, and these materials need to be reinforced. Moreover, to be used in a clinical setting, such materials must undergo effective sterilisation. In this work, a PVA hydrogel reinforced with poly(p-phenylene-2,6-benzobisoxazole) (PBO) nanofibres was submitted to three non-conventional sterilisation methods: microwave (MW), high hydrostatic pressure (HHP), and plasma (PM), in order to evaluate their impact on the properties of the material. Sterilisation was achieved in all cases. Properties such as water content and hydrophilicity were not affected. FTIR analysis indicated some changes in crystallinity and/or crosslinking in all cases. MW was revealed to be the most suitable method, since, unlike to PM and HHP, it led to a general improvement of the materials’ properties: increasing the hardness, stiffness (both in tensile and compression), and shear modulus, and also leading to a decrease in the coefficient of friction against porcine cartilage. Furthermore, the samples remained non-irritant and non-cytotoxic. Moreover, this method allows terminal sterilisation in a short time (3 min) and using accessible equipment.