Poly(ether-ether-ketone) (PEEK) is a known bio-implant material due to its excellent mechanical properties. However, the challenging issue of high friction coefficient limits the PEEK applications. In this article, double-layered hydrogel material was obtained by laser processing, surface sulfonation, and poly(vinyl alcohol) (PVA) casting. Characterizations of FT-IR, XRD, SEM, and 3Dmorphology demonstrate that PVA-LSPEEK hydrogel was achieved successfully. PVA-LSPEEK exhibits an extremely smooth surface with a roughness of 0.079 μm. And this hydrogel presents an excellent mechanical adhesion to PEEK substrate, forming a soft-hard structure. Tribological properties of PVA-LSPEEK are improved drastically when compared to the PEEK substrate. This innovative hydrogel material provides a potential application in articular cartilage defect repair.