A series of statistical random copolymers of dioctylfluorene (DOF) and 3,4-ethylenedioxythiophene (EDOT) were synthesized by Ni (0) mediated polymerization and their light-emitting properties were compared with poly (9,9-di-n-octylfluorene) (PDOF). The synthesized polymers were characterized using UV-vis spectroscopy, TGA, photoluminescence (PL) & electroluminescence (EL) spectroscopy and by conducting molecular weight studies. The resulting polymers were found to be thermally stable and readily soluble in organic solvents. The UV-visible absorption and PL emission spectra of the copolymers were gradually red-shifted as the fraction of EDOT in copolymers increased. Light-emitting devices were fabricated in an ITO (indium-tin oxide)/PEDOT/polymer/Ca/Al configuration. Interestingly, the EL spectra of these devices were similar to the PL spectra of the corresponding polymer film. However, the EL devices constructed from the copolymer showed more than 10 times higher efficiency level than the devices constructed from the PDOF homopolymer. This higher efficiency is possibly the result of better charge carrier balance in the copolymer systems due to the lower HOMO levels of the copolymers in comparison to that of PDOF homopolymer.