In this work, the reaction of crotonaldehyde ethinylation was studied for the first time using complex catalytic systems prepared based on trifluoromethylsulfonate salts of some d-group metals. Aliphatic and aromatic alkynes were used as ethinylating agents. The processes were carried out in various solvents, and the corresponding acetylene alcohols were synthesized. The influence of reagents, substrates, catalysts, and solvents on the rate, direction, and yield of reaction products was studied. The most optimal conditions for the synthesis of acetylenic alcohols were found. A series of relative catalytic activities of the selected catalysts was developed. Using modern physical and chemical research methods, the synthesized acetylene alcohols were identified, and their specific constants, structures, purity, and composition were confirmed.