A series of palladium acetylide complexes with the structures of Pd(PPh3)(2)(CdropCR)(2) (R = C(CH3)(2)OH, CH2OCOCH3, CH2OH, p-C(6)H(4)CdropCH, C6H5) were developed for homogeneous copolymerization of polar with non-polar alkynes. The catalytic activity of the five palladium acetylide complexes towards copolymerization of propargyl alcohol (OHP) with p-diethynylbenzene (p-DEB) is compared and discussed. The complexes containing polar alkynyl ligands show higher activity than corresponding complexes containing non-polar ligands. Solvent systems exhibit significant influence on realizing homogeneous polymerization and obtaining soluble copolymer. The copolymerization of OHP with p-DEB initiated with these catalysts could proceed under mild conditions to give soluble pi-conjugated copolymer in yields as high as 66%. Features for copolymerization of OHP with p-DEB using Pd(PPh3)(2)(CdropCCH(2)OH)(2) in CHCl3/MeOH mixed solvents have been described. (C) 2002 Elsevier Science B.V. All rights reserved.