Copolymers of 2,3,4,5,6-pentafluorostyrene (PFS) having a combination of high hydrophobicity and high glass transition temperature (T-g) are reported here for the first time. The copolymerization was carried out using N-phenylmaleimide (NPM) as the comonomer and azobisisobutyronitrile (AIBN) as the initiator under both conventional thermal heating and microwave heating. The initial copolymerization rate was found to be higher under microwave heating than under thermal heating. The copolymerization parameters were determined using the Fineman-Ross method and were found to be r(1) (NPM) = 0.28 and r(2) (PFS) = 0.86. Increased incorporation of NPM in the copolymers led to an increase in Tg of the copolymers without significantly affecting the hydrophobicity of poly(2,3,4,5,6-pentafluorostyrene). Thermal stability of the copolymers is also reported. (c) 2005 Society of Chemical Industry.