The fretting corrosion behavior of zirconium (Zr) alloy under different pH conditions was investigated. The morphology, microstructure, and wear mechanism of Zr alloy under different pH condition was analyzed. The results indicate that the wear scar Zr alloy in acid condition presents a typical feature of wear debris, furrow, and delamination, indicating that the wear mechanism is oxidation wear and abrasive wear. The microstructure beneath the wear scar is composed of a thick wear debris layer (WDL), deformation layer (DL), and thin tribologically transformed structure (TTS). The WDL is a nano-sized grainy structure and the micro-crack is mainly formed on the interface of WDL and TTS. The largest wear volume belongs to the wear scar in pH of 1 condition. Because the corrosion and corrosion induced by wear would destroy the surface protective film and form a thick WDL, which is easy to separate to increase the material loss volume. The Zr alloy in pH of 1 condition shows the largest volume ratio of wear induced by corrosion and corrosion induced by wear.