Long reaction period (dozens of hours) is often required for the synthesis of conjugated polymers by palladium-catalyzed Suzuki polymerization reaction. This work shows that microwave can accelerate Suzuki polymerization to realize the ultra-rapid synthesis of conjugated polymers, here poly(9,9-dihexylfluorene)s (PDHFs) as an example. The effects of reaction conditions on the polymerization have been systematically investigated, including the mode of microwave irradiation, microwave power, reaction temperature, reaction time, solvents, catalyst species, and catalyst concentrations. Compared with the conventional heating method (oil bath) for the synthesis of PDHFs (48 h, Mw = 20,000 g/mol), Suzuki polymerization under optimized microwave condition can yield PDHFs with higher molecular weight (Mw = 40,000 g/mol) in a much shorter time (14 min). The structures of obtained PDHFs samples are fully characterized spectroscopically, demonstrating well-defined PDHFs have been prepared through microwave-assisted (MA) Suzuki polymerization reaction. In addition, the mechanism of MA Suzuki polymerization is proposed preliminarily. (c) 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013, 51, 1950-1955