Exploring high efficient and durable electrocatalysts at low cost for the oxygen reduction reaction (ORR) in fuel cells or metal-air battery to replace precious-metal ones such as platinum (and its alloy) has triggered extensive research interests. Recently, continuous efforts have been made to fabricate doped graphene as ORR electrocatalysts and N-doped graphene is a promising candidate for replacing Pt-based catalysts because of its high ORR catalytic activity, long-term stability, negligible fuel crossover effect, and low cost. In this study, we conducted a one-step method to synthesize N-, P-, S-tridoped graphene (denoted as CNPS) as ORR metal-free electrocatalyst with the acephate as the dopants. The XPS analysis confirms that N, P, S heteroatoms have been successfully doped in graphene sheet and the electrochemical characterization results reveal that the tridoped graphene exhibits efficient ORR activity.