In bulk heterojunction (BHJ) solar cells, the buffer layer plays a vital role in enhancing the power conversion efficiency (PCE) by improving the charge carrier dynamics. A comprehensive understanding of the contacts is especially essential in order to optimize the performance of organic solar cells (OSCs). Although there are several fundamental reports on this subject, a proper correlation of the physical processes with experimental evidence at the photoactive layer and contact materials is essential. In this work, we incorporated three different additional buffer layers, namely, tris(8-hydroxyquinolinato) aluminum (Alq3), bathophenanthroline (BPhen) or bathocuproine (BCP) with LiF/Al as conventional cathode contact in both rrP3HT:PC61BM and rrP3HT:PC71BM blend BHJ solar cells and their corresponding photovoltaic performances were systematically correlated with their energy level diagram. The device with dual cathode buffer layer having ITO/PEDOT:PSS/blend polymer/BCP/LiF/Al configuration showed the best device performance with PCE, η = 4.96%, Jsc = 13.53 mA/cm2, Voc = 0.60 V and FF= 61% for rrP3HT:PC71BM and PCE, η = 4.5% with Jsc = 13.3 mA/cm2, Voc = 0.59 V and FF = 59% for rrP3HT:PC61BM. This drastic improvement in PCE in both the device configurations are due to the combined effects of better hole-blocking capacity of BCP and low work function provided by LiF/Al with the blend polymer. These results successfully explain the role of dual cathode buffer layers and their contribution to the PCE improvement and overall device performance with rrP3HT:PCBM based BHJ solar cell.