Tailoring terminated edge of hexagonal boron nitride (h-BN) for enhancing catalysis has turned to be an imperative for the rational design of a highly active aerobic catalyst. Herein, a tailoring N-terminated porous BN (P-BN) strategy is reported with a zinc (Zn) salt as a dual-functional template. The Zn salt acts as both an in situ template and an N-terminated defective edges directing agent. The zinc salt template turns to Zn nanoparticles (Zn NPs) and functions as physical spacers, which are subsequently removed at a higher temperature, for producing P-BN, whose high surface area is high to 1579 m2 g-1 . Moreover, because of the lower electronegativity of Zn, boron (B) atoms are partly replaced by Zn atoms and ultimately preferred to N-terminated edges with the volatilization of Zn NPs. Owing to the moderate dissociative energy of oxygen atoms on N-terminated edges, the N-terminated edges are proved to be the origin of an enhanced aerobic catalytic activity by density functional theory (DFT) calculations. Moreover, the DFT calculation result is experimentally verified.