By engineering the interface between the intermediate photoactive layer and the cathode aluminum (Al) electrode, through the introduction of ultra-thin layers of various materials, in a standard bulk heterojunction (BHJ) polymer solar cell (PSC) fabricated of regioregular poly(3-hexylthiophene) (rr-P3HT) and phenyl-C61-butyric acid methyl ester (PCBM), the power conversion efficiency (PCE) has been effectively improved. The devices fabricated using individual single interlayer of bathocuproine (BCP), lithium fluoride (LiF) and Buckminster fullerene C60 have shown optimal efficiencies of ~2.40%, ~3.21% and ~1.92% respectively. Further improvement of the photovoltaic efficiency was achieved by introducing a composite bilayer made of LiF in combination with BCP as well as with C60 at the BHJ/cathode interface. The best results were obtained by interposing a 9 nm of C60 interlayer in combination with a 0.9 nm thick LiF layer, with the PCE of the PV cells being effectively increased up to 3.94% which represents an improvement of 23% as compared to the standard device with LiF interlayer alone. The photocurrent density (Jsc) versus voltage (V) characteristic curves shows that the increase of the efficiency is essentially due to an increase in Jsc. Moreover, all the sets of devices fabricated using various interlayers over a certain range of thickness exhibit an optimum PCE that is inversely proportional to the series resistance of the PV cells. We presume that interposing a C60/LiF layer at the interface could repair the poor contact at the electron acceptor/cathode interface and improve the charge career extraction from the BHJ.