Random copolymers, PFDEP13 and PFDEP26, were synthesized through Ni(0)-mediated polymerization with 2,7-dibromo-9,9-di-n-hexylfluorene and 1-[2-(2,5-dibromo-4-{2-[4-(2-ethylhexyloxy)phenyl]vinyl}phenyl)vinyl]-4(2-ethylhexyloxy)-benzene (DEP). The resulting polymers are soluble in aprotic polar organic solvents and show good thermal stability up to ca. 400degreesC. The photoluminescence (PL) emission peaks of the two copolymers are red-shifted with respect to that of common polyfluorene (PF) homopolymer. Both the EL spectra of PFDEP13 and PFDEP26 show maximum emission peaks at 470 nm. In particular, PFDEP26 exhibits a broad emission spectrum in the whole visible region, which suggests the possibility of PFDEP26 as a white-light-emitting polymer.