Room temperature Suzuki cross-coupling polymerization of aryl dibromides/diiodides with aryldiboronic acids/acid esters with t-Bu3P-coordinated 2-phenylaniline-based palladacycle complex, [2 '-(amino-kN)[1,1 '-biphenyl]-2-yl-kC]chloro(tri-t-butylphosphine)palladium, as a general precatalyst is described. Such room temperature Suzuki cross-coupling polymerization is achieved by employing six equivalents or more of the base and affords polymers within an hour, with the yields and the molecular weights in general comparable to or higher than reported results that required higher reaction temperature and/or longer polymerization time. Our study provides a general catalyst system for the room temperature Suzuki cross-coupling polymerization of aryl dibromides/diiodides with aryldiboronic acids/acid esters and paves the road for the investigation of employing other monodentate ligand-coordinated palladacycle complexes including other electron-rich monophosphine-coordinated ones for room temperature cross-coupling polymerizations. (c) 2019 Wiley Periodicals, Inc.