The effectiveness and mechanism of permanganate enhancing arsenite (As(III)) co-precipitation with ferric chloride is investigated. Effects of parameters such as pH, natural organic matter (NOM) on As removal are studied. Permanganate significantly enhances As(III) removal for ferric co-precipitation (FCP) process. With Fe(III) dosage increasing from 2mg/L to 8mg/L, As removal increased from 41.3% to 75.4% for FCP process; for permanganate oxidation-ferric co-precipitation (POFCP) process, however, corresponsive As removal increased from 61.2% to 99.3% . As removal increased with higher pH for both processes; comparing to FCP process, pH had less effects on As removal for POFCP process; the presence of NOM reduced As removal for FCP process whereas no obvious reduction was observed for POFCP process. Permanganate oxidizing As(III) to As(V) is the main course for enhancing As(III ) removal; furthermore, products of permanganate reduction, hydrous MnO2 (s), also contribute to removing As. POFCP process exhibits good potential of removing As(III ) to assure chemical safety of drinking water.