Catalytic performance and NaBH4 utilization are two crucial concerns in the electrooxidation of NaBH4. To improve the inherent properties of regular performance and low fuel utilization of the transition metal Co and Ni, an efficient anode catalyst of ultra-thin CoNi nanosheets modified novel 3D self-supported reduced graphene oxide foam is prepared in this work. The alkaline condition borohydride oxidation reaction on the prepared catalyst is investigated in a typical three-electrode system. The prepared catalyst shows a high performance due to the large electrochemical active surface area, low activation energy (8.29 kJ.mol(-1)), and the small electrochemical impedance it embraced. Linear scan voltammetry recorded in a low concentration of NaBH4 suggests that borohydride oxidation is a first-order reaction on the prepared catalyst. Based on the unique structure of the catalyst, which is useful to capture the hydrogen and perform further oxidation of hydrogen, higher utilization of NaBH4 achieved on the catalyst. Besides, the prepared anode catalyst applied to a direct borohydride-hydrogen peroxide fuel cell (DBHPFC). The results of polarization curve and power density curves, as well as stability research, all indicate that the as-prepared catalyst is a highly efficient anode material for application in DBHPFC.