A new synthetic route to polytriarylamines by microwave-assisted palladium-catalysed amination between 2,4-dimethylaniline and 4,4'-dibromobiphenyl is reported. The use of microwave heating significantly reduces the polymerisation time from days to around five minutes when conducted at 100 degrees C. However, prolonged microwave irradiation (20 min) can cause chain degradation of these polymers. Reactive amino and bromo end-groups can be removed by sequential reaction with 4-bromoanisole and diethylamine to generate polytriarylamines that are suitable for the fabrication of organic electronic devices.