Polymeric composites based on the copolymer - octyl methacrylate:acrylonitrile (1:1) with incorporated azo dyes: [4-((E)-{4-[(E)-(4-nitrophenyl)diazenyl]phenyl}diazenyl) phenyl]amine, 1-[4-((E)-{4-[(E)-(4-amino phenyl)diazenyl]phenyl}diazenyl)phenyl] ethanone, 4-((E)-{4-[(E)-(4-aminophenyl)diazenyl] phenyl}diazenyl)benzoic acid and its complex with Co were synthesized and their electro-optical properties were investigated. The influence of the electric field on the absorption spectra of new polymer composites with azodyes and complex was investigated. The influence of electronic nature of substitutes in the bisazo chromophores on the electro-optical effect was investigated.