Cobalt phosphide (CoP) has aroused extensive research interest in a field of electrochemical application due to its excellent catalytic activities. CoP and its compounds have been widely reported using in hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). However, few reports about CoP as electrocatalysts for oxygen reduction reaction (ORR) were presented. In this work, we prepare reduced graphene-oxide(rGO)-loaded CoP (rGO@CoP) as an electrocatalyst for ORR through in situ hydrothermal treatment. The rGO@CoP as ORR catalyst exhibits excellent activities where its onset potential has a positive increase of 129[Formula: see text]mV, and the ORR potential achieves an increase of 330[Formula: see text]mV at a current density of 1.0[Formula: see text]mA[Formula: see text]cm[Formula: see text] compared with that of pure CoP. The current density is also significantly improved with an increase of 0.51[Formula: see text]mA[Formula: see text]cm[Formula: see text] at [Formula: see text]350[Formula: see text]mV, and the Tafel slope has a decrease of 19[Formula: see text]mV dec[Formula: see text]. Further tests show that the electron transfer number of rGO@CoP is 3.66, which is larger than 2.19 of pure CoP, indicating that it is dominated by a four-electron transfer pathway. Moreover, its stability (remained 98.6% current after working 6000[Formula: see text]s) and methanol tolerance are outstanding. These results show that rGO@CoP may be considered to replace traditional Pt-based ORR catalysts for fuel cells, and rGO loading has been proven to be an effective strategy to enhance the ORR performance of CoP, which may provide a new idea to synthesize transition metal phosphides as ORR catalysts.