Batch experiments were conducted to investigate the influence of pH on Cr(VI) reduction with Fe(II), sulfide and mixtures of Fe(II) and sulfide at pH 3.0–12.0. The results showed that Fe(II) could reduce Cr(VI) with a high removal of nearly 100% in the pH range of 3.0–9.0, while the reduction of Cr(VI) decreased to approximately 60% considering the oxygenation of Fe(II) at pH 12.0. The reaction between Cr(VI) and sulfide, however, was largely pH dependent. H2S was the main sulfide species with the Cr(VI) removal of ∼80% at pH < 7.0, while sulfide mainly existed in the forms as HS− or S2− at pH ≥ 7.0, which had very limited removal of Cr(VI) (no more than 10%). The Cr(VI) removal by the mixtures of Fe(II) and sulfide was also compared with the sum of separate ones at different pH values. The sum of Cr(VI) removal by single Fe(II) and S(-II) was similar to that by the mixtures at pH 3.0–5.0 and pH 12.0, while the removal of Cr(VI) by the mixtures was observed to be more effective than the sum of the single-species removals at pH 7.0–9.0; the promoting effect was primarily attributed to the catalysis of ferric ion generated during the reduction process.