In this study, the enhanced effect of pyrite (FeS2) on zero-valent iron (Fe0) corrosion for arsenic (As) removal was investigated in a combined-Fe0/FeS2 system. The effects of different Fe0/FeS2 composition, dosage and initial pH were evaluated by batch experiments. Results showed that the best combination ratio of Fe0:FeS2 (w/w) was 1:1 and the optimal dosage of mixture was 2.0 g/L. The combination of Fe0 and FeS2 in a system significantly enhanced the reactivity of Fe0 for effective As removal within a broad pH range (3.0-9.0). The effective As removal in the combined-Fe0/FeS2 system was primarily ascribed to being enhanced corrosion of Fe0 by addition of FeS2. SEM and XRD characterizations strongly verified this point. Specifically, the mechanism study (the releases of Fe2+ and total Fe ion, variations of pH values as well as XPS characterization) suggested that FeS2 in the combined-Fe0/FeS2 system could alleviate the passivation of Fe0 (pHini 3.0-5.0) and accelerate the dissolution of pristine oxide film that coated on Fe0 surface (pHini 6.8-9.0). Besides, FeS2 in combined-Fe0/FeS2 system could also accelerate the reactions between Fe0 to O2 at pHini 3.0-9.0. These phenomena were well explained by a galvanic couple between Fe0 and FeS2, where FeS2 was a cathode and Fe0 was an anode. Consequently, electrons released from Fe0 that mediated by FeS2 to oxide film, passivation layer and O2 were accelerated in combined-Fe0/FeS2 system and thereby enhanced the corrosion of Fe0 for efficient As removal. Our findings suggest that utilizing FeS2 to enhance the corrosion of Fe0 would be a promising technology for remediation of As-contaminated water.