We investigate the effect of anode buffer layers (ABLs) on the performances of multi-layer heterojunction solar cells with thienylenevinylene-triphenylamine with peripheral dicyanovinylene groups (TDCV-TPA) as donor material and fullerene C-60 as acceptor. The deposition of a CuI layer between the ITO anode and the electron donor significantly improves the short-circuit current density (J(sc)) and fill factor (FF) but reduces the open-circuit voltage (V-oc). On the other hand, a MoO3 buffer layer increases the V-oc but leads to limited J(sc) and FF values, thus reducing power conversion efficiency (PCE). In this context, we show that the use of a hybrid anode buffer layer MoO3/CuI leads to a considerable improvement of the cells performances and a PCE of 2.50% has been achieved. These results are discussed on the basis of the dual function of MoO3 and CuI. While both of them reduce the hole injection barrier, CuI improves the conductivity of the organic film through an improvement of molecular order while MoO3 prevents leakage current through the diode. Finally the results of a cursory study of the ageing process provide further support to this interpretation of the effects of the various buffer layers. (C) 2012 Elsevier B.V. All rights reserved.