Knowledge of frictional evolution and associated damage mechanism during sliding wear conditions using binderless WC-based cemented carbide is lacking. In this study, the frictional evolution and corresponding transformation of microstructure, and wear mechanisms of Al2O3/WC-based cemented carbide due to the effect of different contact pressure, especially high pressure have been explored using a reciprocating ball-on-flat sliding wear tester, which was experimentally simulated following the ASTM G133–02 standard. The dynamic curves in friction coefficient with the sliding time were described. The microscopic 3D topography of contact surface was obtained by the MFP-3D atomic force microscope. The material removal and the wear rate were discussed. Worn surface morphologies at different moments, cross-sectional images of wear tracks at different loads, and wear debris were taken by field emission scanning electron microscope. The results suggested that the pressure plays a decisive role in frictional evolution and wear characteristics. Two models of frictional evolution were declared. A novel “surge” phenomena in friction coefficient was found and explained at high contact pressure. Wear transition from mild wear to severe wear was confirmed. More than one wear mechanism was observed, including micro-cutting (polishing), generation and propagation of cracks, cracking-induced spalling, plastic deformation, and the formation of tribolayer.