In previous work, we have reported that a P3HT:PCBM-based organic photovoltaic cell using a thermally evaporated DMDCNQI buffer layer shows a high power conversion efficiency. In the present work, we have fabricated organic photovoltaic cells consisting of ITO/PEDOT:PSS/P3HT:PCBM:DMDCNQI/DMDCNQI/Al using an all-solution process. A thin, uniform DMDCNQI film was obtained in a methanol solution with high solubility and low viscosity. The prepared device shows a high power conversion efficiency of 2.9%. In particular, a maximum external quantum efficiency of 81% was obtained.