Polyethylene glycol 600 (PEG 600) and polysorbate 20 (Tween 20) were used as a composite corrosion inhibitor of zinc in alkaline solution for the first time. The effects of the composite and individual inhibitors on corrosion inhibition of zinc were evaluated by weight-loss analysis and electrochemical methods including potentiodynamic, potentiostatic, and electrochemical impedance spectroscopic measurements. It was found that there was a synergistic effect between PEG 600 and Tween 20 on corrosion inhibition of zinc. The corrosion inhibition efficiency of the composite inhibitor, 500 ppm PEG 600 + 500 ppm Tween 20, was 89%, much higher than that of the individual inhibitor, 1000 ppm Tween 20 (71%) or 1000 ppm PEG 600 (55%). The battery (Zn/MnO2) discharge performance tests showed that the composite inhibitor reduced the self-discharge of zinc anode more effectively than the individual inhibitor. The synergistic mechanism between PEG 600 and Tween 20 was discussed.