Polytetrafluoroethylene/poly(methyl methacrylate) (PTFE/PMMA) composites were prepared by a self-curing method. The influence of heat treatment processes on the friction and wear behaviors of PTFE/PMMA composites against bearing steel balls were studied by a ball-on-disk tribometer. The thermal performance of PTFE/PMMA composites with heat treatment was analyzed by Thermogravimetric Analysis (TGA). The surface morphologies and element distribution of PTFE/PMMA composites in a PMMA matrix were detected by Field Emission Scanning Electron Microscopy (FE-SEM) and Energy Dispersive Spectroscopy (EDS). The results indicated that the wear rates of PTFE/PMMA composites with different heat treatments significantly declined compared with the unheated treatment composite. The wear rate of the PTFE/PMMA composite decreased firstly and then increased with molding temperature and time increasing, and reduced with the molding pressure increasing. The main wear mechanisms of PTFE/PMMA composites with different heat treatments were fatigue wear and abrasive wear.