Polytriarylamine copolymers can be prepared by Suzuki Miyaura cross-coupling reactions of bis N-methyliminodiacetic acid (MIDA) boronate ester substituted arylamines with dibromo arenes. The roles of solvent composition, temperature, reaction time, and co-monomer structure were examined and (co) polymers prepared containing 9, 9-dioctylfluorene (F8), 4-sec-butyl or 4-octylphenyl diphenyl amine (TFB), and N, N- bis(4-octylphenyl)- N, N'- diphenyl phenylenediamine (PTB) units, using a Pd(OAc)(2)/2-dicyclohexylphosphino- 20,60-dimethoxybiphenyl (SPhos) catalyst system. The performance of a di-functionalized MIDA boronate ester monomer was compared with that of an equivalent pinacol boronate ester. Higher molar mass polymers were produced from reactions starting with a difunctionalized pinacol boronate ester monomer than the equivalent difunctionalized MIDA boronate ester monomer in biphase solvent mixtures (toluene/dioxane/water). Matrixassisted laser desorption/ionization mass spectroscopic analysis revealed that polymeric structures rich in residues associated with the starting MIDA monomer were present, suggesting that homo-coupling of the boronate ester must be occurring to the detriment of cross-coupling in the step-growth polymerization. However, when comparable reactions of the two boronate monomers with a dibromo fluorene monomer were completed in a single phase solvent mixture (dioxane+ water), high molar mass polymers with relatively narrow distribution ranges were obtained after only 4 h of reaction. (C) 2017 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc.