Form a green and sustainable chemistry point of view, cross-dehydrogenative coupling (or oxidative cross-coupling) reactions have been recognized as environmentally sustainable and atom economical synthetic routes for the construction of new carbon-carbon and carbon-heteroatom bonds, since no pre-functionalization of starting materials is required. In the past few years, the direct coupling of sp-hybridized C-H bonds with heteroatom-H bonds has received much attention because of the importance of heteroatom-substituted alkynes in organic and medicinal chemistry. This review examines the recent developments in cross-dehydrogenative coupling reactions between C(sp)-H and X-H (X = N, P, S, Si, Sn) bonds, with a particular focus on the mechanistic aspects of the reactions.