As an environmentally friendly oxidant, H2O2 is widely utilized in various fields; however, its production methods remain limited to the chemical anthraquinone process. Alternatively, electrocatalytic oxygen reduction possesses numerous notable advantages (e.g., cost-effectiveness, small-scale, and distributed nature). As electrocatalytic oxygen reduction has been widely investigated in the fields of fuel cells and metal-air batteries, the mechanism of the 2e−-ORR pathway for producing H2O2 is not sufficiently clear. Herein, we explore the effect of the cobalt (Co) coordination environment on the electrochemical production of H2O2. The detailed investigation on N-, P-, and S-coordinated Co catalysts (Co1N1N3, Co1P1N3, and Co1S1N3) demonstrates that changing the coordination environment evidently affects the H2O2 selectivity, and the S-coordinated Co exhibits the best catalytic performance. This finding would lead to the design and selection of catalysts at atomic level for producing H2O2 via electrocatalytic oxygen reduction.