A monomer having dibenzothiophene moiety, 2-vinyldibenzothiophene (1), was prepared by the Ni-catalyzed cross-coupling reaction of vinyl bromide with the Grignard reagent of 2-bromodibenzotkiophene. The radical homopolymerization of 1 and the copolymerization with styrene were carried out at 60 degrees C in toluene (1.0M) for 20 h using AIBN (5 mol %) as an initiator to obtain the corresponding polymers in high yields. Thermal analyses of the copolymers showed that both 10% weight loss and glass transition temperatures increase when increasing the content of 1 unit. The monomer reactivity ratio was evaluated as r(1) = 2.55 (1) and r(2) = 0.16 (styrene).