Hydrogels are ideal substitute materials for articular cartilage. The fretting wear behavior of polyvinyl alcohol (PVA) hydrogel and three types of PVA-based composite hydrogels under dry friction condition is investigated experimentally. Polyvinyl pyrrolidone (PVP), graphene oxide (GO), and multi-walled carbon nanotubes (MWCNTs) are mixed into PVA hydrogels as additives to prepare three composite hydrogels. A sphere-on-flat contact model is established between the PVA-based hydrogel coating and a stainless steel ball. The reciprocating fretting wear equipment is used to conduct fretting tests. Surface wear morphology and wear depth are characterized using three-dimensional (3D) ultra-depth of field microscopy and 3D white-light interference profilometer. The impacts of displacement amplitude, normal force, exposure time, and the number of freeze–thaw cycles on fretting wear behavior of four PVA-based hydrogels are investigated. The results show that the PVA/MWCNTs composite hydrogel exhibits the highest friction coefficient and relatively good wear resistance.