Surface oxygen vacancies in defective metals have the capacity to enhance oxygen evolution reaction (OER) activity but easily suffer from instability and deactivation in continuous electrocatalysts. Heterojunction engineering is important for achieving effective catalysis, but its simultaneous engineering remains a challenge. Therefore, it is necessary to develop an effective heterojunction catalyst to improve the electrocatalytic stability of defective metallic oxygen vacancies. In this work, we report a Ce, Mo bimetallic defective heterojunction P-MoO3/Ce2Mo4O15@NF-1 via a facile one-step hydrothermal method and annealing in a tube furnace. Bimetallic oxide heterojunctions offer several advantages over conventional single-metal heterojunctions, including greater stable structure, more active sites, faster rates of electron transfer, and less pollution of the environment. Meanwhile, P-doping could enhance the metallicity significantly. In addition, the prepared catalysts P-MoO3/Ce2Mo4O15@NF-1 showed extraordinary catalytic activity for OER in alkaline media. The overpotential and Tafel slope of the catalyst at a current density of 50 mA cm-2 were 270 mV and 87.27 mV dec-1, respectively. It maintains an impressive balance between electrocatalytic activity and stability. This research explores the co-effects of Ce and Mo bimetallic oxide in defective electrocatalysts and also provides ideas for designing OER catalysts with defective metal heterojunctions.