Comprehensive SummaryAn unprecedented copper nitrate‐mediated bond cleavage of alkynes was developed for the modular synthesis of isoxazoles, where either C–S bond or C≡C triple bond was cleaved selectively. Substituents attached to the C≡C triple bonds could differentiate the chemical bonds cleavage and reaction pathways disparately. Various transformations of products illustrate promising applications of the given protocols.This article is protected by copyright. All rights reserved.