A Pd/Pt-Bu-3 catalyst having bulky, electron-rich ligands significantly outperforms conventional "step-growth catalysts" Pd(PPh3)(4) and Pd(Po-Tol(3))(3) in the Suzuki polycondensation of the AB-type arylene-based monomers, such as some of the substituted fluorenes, carbazoles, and phenylenes. In the AA+BB polycondensation, Pd/Pt-Bu-3 also performs better under homogeneous reaction conditions, in combination with the organic base Et4NOH. The superior performance of Pd/Pt-Bu-3 is discussed in terms of its higher reactivity in the oxidative addition step and inherent advantages of the intramolecular catalyst transfer, which is a key step joining catalytic cycles of the AB-polycondensation. These findings are applied to the synthesis of a carbazole-based copolymer designed for the use as a hole conductor in solution-processed organic light-emitting diodes.