Polymerizations of 1,2-diisocyanobenzenes to afford poly(quinoxaline-2,3-diyl)s were investigated in the presence of various metal salts and their phosphine complexes, whereby especially the stable and easily-accessible [NiCl2(PMe3)(2)] was found to exhibit a high polymerization activity. The end groups of the resulting polymers were determined by mass spectrometry measurements as -P+Me3 and -H, indicative of a nucleophilic attack of PMe3 towards an isocyano group as the initial step of the polymerization. A chiral polymer ligand, prepared by such a [NiCl2(PMe3)(2)]-mediated polymerization, demonstrated high enantioselectivities in palladium-catalyzed asymmetric hydrosilylation reactions, suggesting that the polymeric catalyst adopted a single-handed helical backbone.