It is still a huge challenge to find nonnoble-metal oxygen reduction reaction (ORR) catalysts that can replace Pt. Here, we report a heterostructure Ni(OH)2/ZrO2 catalyst made in one step using a simple alcohol thermal method that has the same onset potential (0.84 V) and overpotential (390 mV) as 20% Pt/C, abundant active sites, low Tafel slope (57 mV dec–1), good stability and excellent methanol tolerance. Moreover, we found that ZrO2 has a great influence on Ni(OH)2 through its abundant oxygen vacancies and inhibits the oxidation of Ni2+. However, the nature of its excellent catalytic performance is still unclear, so we analyzed it using a density functional theory (DFT) calculation. In particular, we studied the heterostructure Ni(OH)2/ZrO2 due to the abnormal synergistic effect of charge transfer and heterostructure interface and stabilized O radicals using ZrO2, which promoted the spontaneous progress of the Ni(OH)2/ZrO2 ORR, thereby improving the catalytic performance.