We have developed a new series of single-component air- and moisture-stable catalysts for alkyne polymerization based on chloro-nickel and chloro-cobalt complexes containing phosphine ligands. The polymerization of p-diethynylbenzene initiated by these complexes proceeds smoothly in the presence of amines at room temperature to afford soluble pi-conjugated polymers in yields as high as 81% with weight-average molecular weight up to 17 600.