The preparation of double-cable polymers, which consist of a hole conducting conjugated chain carrying pendant electron accepting/conducting moieties, is a promising strategy to prevent donor/acceptor phase segregation and to achieve defined microscopic structure in organic bulk heterojunction solar cells. In this paper we report the electrochemical synthesis and the investigation of a double-cable consisting of a polythiophene backbone bearing, via covalent bonds, electron accepting tetracyanoanthraquinodimethane (TCAQ) type moieties. Electrochemical studies and UVVIS absorption spectroscopy reveal, that in dark, the polythiophene chain and the TCAQ moieties retain their individual ground-state properties. Upon illumination photoinduced electron transfer occurs, which is studied by photoinduced VIS-NIR absorption spectroscopy.