2-Mercapto benzimidazole (MBI) was used as a copper corrosion inhibitor in aerated 0.5 mol L-1 H2SO4 solutions. The inhibition efficiency (IE) increased with increasing MBI concentration to 74.2% at the 1 mM level. A synergistic effect existed when MBI and iodide ions were used together to prevent copper corrosion in sulfuric acid. It was found that IE reached 95.3% in 0.5 mol L-1 H2SO4 solutions containing 0.75 mmol L-1 MBI and 0.25 mmol L-1 KI. X-ray photoelectron spectroscopy (XPS) analysis of the copper samples showed that a (Cu+ MBI) complex film formed on the surface to inhibit the copper corrosion and the iodide ions did not participate in the formation of the inhibitor film. The synergistic effect was attributed to the adsorption of iodide anions on the copper surface, which then facilitated the adsorption of protonated MBI and the formation of an inhibitive film.