The use of (N-heterocyclic carbene)-palladium complexes as precatalysts for the synthesis of poly(triarylamine)s by C-N coupling is reported. Effective control of the molecular weight distribution by in situ end-capping during the polymerization was found to be important for application of these polymers as the charge transporting layers of OFETs. (C) 2012 Elsevier Ltd. All rights reserved.