This review surveys carbon-carbon bond forming reactions of acetylene radical-cations, generated under the one-electron oxidation of alkynes in the systems lead dioxide (PbO₂)-strong acid (CF₃CO₂H, FSO₃H, HF). The oxidative dimerization proceeds very regioselectively at acetylene carbons. This approach is a powerful synthetic tool, leading to complex and polyfunctional organic molecules, such as, dicarbonyl-and tetracarbonyl-substituted ethylenes, 1,4-difluoro-and 1,4-dichlorobutadienes, etc. Reaction mechanisms of acetylene radical-cations are considered. The reactivity of acetylene radical-cations may be explained by their electronic structure, determined by means of electron spin resonance spectroscopy and cyclic voltammetry.