The influences of various geochemical factors, such as pH, phosphate, bicarbonate, humic acid, permanganate, and dissolved oxygen, on hexavalent chromium(Cr(VI)) removal by zero-valent iron(Fe0) were investigated in a batch setting. Results showed that low pH environments were favorable to removal of Cr(VI) compared with high pH environments. Phosphate significantly inhibited removal of Cr(VI) possibly due to competition of adsorption sites on corrosion products. Humic acid introduced a marginal influence on Fe0 reactivity toward Cr(VI) reduction, whereas bicarbonate enhanced Cr(VI) removal by maintaining the solution pH near neutral. Permanganate cumbered the removal of Cr(VI) due to its competition for electron from oxidation of Fe0. The removal efficiency of Cr(VI) was higher in oxic conditions than that in anoxic conditions.