The present work focuses on a theoretical investigation of mechanistic features, chemoselectivity, regioselectivity, and effect of substituents in the gold-catalyzed reactions of alkynyl thioethers and isoxazoles. The DFT calculations reveal that the nucleophilic attack of isoxazole to a β-position of catalyst-bound ynamide forms a vinyl intermediate. This undergoes cleavage of the N-O isoxazole bond and isomerizes to form an α-imino α'-sulfenyl gold carbene complex with stabilization of the Au-S interaction. For 3,5-dimethylisoxazole, the reaction follows a formal [3 + 2] cycloaddition pathway and a 1,3-H migration to give the pyrrole products. Replacement of 3,5-dimethylisoxazole by 3,5-dimethyl-4-phenylisoxazole leads to the formation of deacylative annulation products and desulfenylated 3-acylated pyrroles. Reactions with 4-methyl-3,5-diphenylisoxazoles induce the formation of N-acylated pyrroles and desulfenylated 3-acylated pyrroles. For the minor pathway, the α-addition and 1,2-S migration result in sulfur-substituted β-keto enamide derivatives. In addition, the unique features of regio- and chemoselectivity were rationalized by the distortion and interaction analysis. Apart from fully rationalizing the experimental results, the theoretical DFT data give an important support for comprehending related types of reaction mechanisms.