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. 400°C. 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.