Zinc molybdate (ZMO) is a safe and effective grafting material for anticorrosion. Herein, we reported the synthesis of ZMO/h-BN with the labyrinth of capillary pores owing to the in situ growth of ZMO on flake hexagonal boron nitride (h-BN) using the hydrothermal method. The special morphological structure provided a tortuous path for aggressive species to the steel substrate, which extended and blocked the transmission of aggressive species, enhancing the physical corrosion barrier performance. In addition, the capillary pores of ZMO contributed to the competitive adsorption of Cl- in an electrolyte and reduced the diffusion of aggressive species, thus further delaying the corrosion process. Moreover, the capture of oxygen by forming a B-O bond with h-BN and the formation of a molybdate passive film are beneficial for the inhibition of cathodic and anodic reactions. As verified by electrochemical impedance spectroscopy (EIS), the anticorrosion performance of ZMO/h-BN coating increased by 49.58% and 130.72% compared with ZMO and epoxy resin (EP) coatings after immersing in a NaCl aqueous solution (3.50 wt%) for 72 h. This coating matrix provides an avenue for molybdate-based corrosion remediation.