New aliphatic-aromatic polymers based on perylene or/and naphthalene diimide units were synthesized and investigated. The effect of diimide core on electrochemical, spectroelectrochemical (UV-vis, EPR) and emission properties was evaluated. Based on cyclic voltammetry measurements the electron affinity of synthesized polymers was estimated. It ranges from - 4.28 to - 4.14 eV which suggests that obtained materials have low-lying LUMO level and could be used in air-operating devices. Investigated polymers show also fluorescence in solution as well as in solid state as a blend with PMMA with quantum efficiency reached up to 68%.