Oxidative carbonylation reactions are powerful methodologies for producing carbonyl derivatives, which show advantages such as wide source of raw materials and a diverse range of products. In recent years, with the concept of environmental protection deeply rooted, developing efficient and green oxidative carbonylation reactions with carbon monoxide and oxygen as reactants, attracts much interest in this field. The C(sp)-H bonds of terminal alkynes exhibit excellent reactivity in oxidative carbonylation reactions, which could form a series of unsaturated carbonyl compounds. This review introduces the oxidative carbonylation reactions of terminal alkynes and their applications in total synthesis, including oxidative alkoxycarbonylation, oxidative aminocarbonylation, and oxidative carbonylation-cyclization, with the focus on the reaction mechanism of carbonylation and metal oxidation. Finally, the future development trends of this field are prospected.