We introduced nanoscale interfacial layers between the PV layer and the cathode in poly (3-hexylthiophene):methanofullerene bulk-heterojunction polymer photovoltaic (PV) cells. The nanoscale double interfacial layers were made of ultrathin poly (oxyethylenetridecylether) surfactant and low-work-function alloy-metal of Al:Li layers. It was found that the nanoscale interfacial layers increase the photovoltaic performance, i.e., increasing short-circuit current density and fill factor with improved device stability. For PV cells with the nanoscale double interfacial layers, an increase in power conversion efficiency of $4.18{pm}0.24%$ was achieved, compared to that of the control devices ($3.89{pm}0.08%$) without the double interfacial layers.