<p>Selective cleavage and functionalization of C-C triple bonds provide a significant opportunity to edit molecular skeletons through unconventional routes. However, the inherent nature of C-C triple bonds and their complex reaction patterns make this process challenging. Here, we demonstrate that commercial nitrates can initiate the aerobic oxidative cleavage of C-C triple bonds to form ester groups. A diverse range of alkynes can be selectively converted into esters with good functional group tolerance. The combination of experimental and theoretical investigations reveals that the unusual reaction process is initiated by oxygen atom transfer from nitrate to alkynes and ketones, resulting in the generation of NO_<i>x</i>, which acts as a radical initiator to accelerate the entire transformation. Additionally, the recyclability of nitrogen species renders this approach catalytic.</p>