A perylene cholesteryl-benzoateethynylene co-polymer was synthesized by Sonogashira reaction and characterized by NMR, UV-Vis, static and dynamic fluorescence spectroscopy and cyclic voltammetry. The optical and electrochemical properties in solution are consistent with photoinduced energy transfer from the electron donor conjugated backbone to the electron acceptor perylene substituent Photovoltaic properties are indeed found, even if the performance of the solar cells is quite low due to the formation of aggregates. The incorporation of (6,6)-phenyl C61-butyric acid methyl ester (PCBM), however, increases by an order of magnitude the efficiency of the prototype (from 10(-4) to 10(-3)%) due to both better phase mixing and improved electrical continuity as supported by Atomic Force Microscopy (AFM) and Electrical Force Microscopy (EFM) studies. (C) 2014 Elsevier B.V. All rights reserved.