The palladium-catalyzed polycondensation of aryl diiodides with 1,3-bis(phenylphosphino)propane afforded poly(arylenediphosphine)s in good yields. Treatment of the polyphosphine with elemental sulfur and hydrogen peroxide efficiently converted the polyphosphine into poly(arylenediphosphine sulfide) and poly(arylenediphosphine oxide), respectively. Treatment of the polyphosphines with Pd(II) and Pt(II) yielded corresponding polymer-metal complexes with high metal contents. Application of the polymer-Pd complexes in homogeneous and heterogeneous aryl alkynylation and carbonylation was examined. The polymer-Pd complexes showed good catalytic activity similar to that of the corresponding low molecular weight Pd complex, and reuse of the polymer catalysts was easily achieved.