An efficient electrocatalytic hydrogen storage system using CuCo2O4 supported by Ni foam (CuCo2O4/NF) as a bifunctional electrocatalyst and quinoxaline as a hydrogen storage carrier was developed. Electrochemical tests were conducted at room temperature and atmospheric pressure. The results showed that the conversion and selectivity of hydrogenation reached 93 % and 99 %, respectively, within 3 h at −0.18 V (vs. RHE). Meanwhile, the conversion and selectivity of dehydrogenation both reached 100 % within 20 min at 1.30 V (vs. RHE). Moreover, due to the excellent durability of CuCo2O4/NF, the hydrogenation conversion remained as high as 89 % after 8 cycles.