A new series of single-component air-stable transition metal acetylide catalysts for the polymerization of substituted acetylenes carrying non-polar and polar groups was developed. The catalytic properties of transition metal acetylides are related to transition metals, phosphines and acetylenic ligands. Nickel acetylides show higher catalytic activity towards the polymerization of substituted acetylenes containing non-polar groups, while palladium acetylides show higher catalytic activity towards the polymerization of substituted acetylenes carrying polar groups. Palladium acetylides with PPh3 ligand are efficient catalysts for the polymerization of substituted acetylenes bearing both non-polar and polar groups.