Nitrate is a raw ingredient for the production of fertilizer, gunpowder, and explosives. Developing an alternative approach to activate the N≡N bond of naturally abundant nitrogen to form nitrate under ambient conditions will be of importance. Herein, pothole‐rich WO3 was used to catalyse the activation of N≡N covalent triple bonds for the direct nitrate synthesis at room temperature. The pothole‐rich structure endues the WO3 nanosheet more dangling bonds and more easily excited high momentum electrons, which overcome the two major bottlenecks in N≡N bond activation, that is, poor binding of N2 to catalytic materials and the high energy involved in this reaction. The average rate of nitrate production is as high as 1.92 mg g−1 h−1 under ambient conditions, without any sacrificial agent or precious‐metal co‐catalysts. More generally, the concepts will initiate a new pathway for triggering inert catalytic reactions.