In this report new PPV-PPE copolymers DE 69, DE 11 were compared with the state of the art materials MDMO-PPV and poly(3-alkylthiophenes) (P3DDT, P3OT). The optical band gap energy of the two copolymers DE 69, DE11 is somewhat higher than that one of MDMO-PPV. The electrochemical band gap was found to be lower for DE 69, DE11 related to for MDMO-PPV. The absorption coefficient of the new PPV-PPE copolymers is higher than for MDMO-PPV but in the same order of magnitude. Films from composites of MDMO-PPV/PCBM and DE69 or DE11 with PCBM show a clear photoluminescence quenching effect. At 77 K two kinds of LESR signals were identified, one of polarons (P+.) and one of radical anions of fullerenes. The LESR results show strong differences in kinetics between the separation and recombination processes of photoexcited charge carriers. The relaxation rates of paramagnetic centers were estimated by microwave power saturation experiments. Photovoltaic devices were prepared under ambient conditions on flexible PET-ITO foils with MDMO-PPV/ PCBM (1:3 wt. %) with ηAM1.5 = 2.4% and DE 69/ PCBM (1:3 wt. %) with ηAM1.5 = 1.75% (A=0.25 cm2, Pin = 100 mW/cm2).