By embedding a thin ZnO layer sandwiched between the hole transport and photoactive layers, organic solar cells (OSC) based on poly(3-hexylthiophene) (P3HT) were prepared by spincoating. UV–vis spectra of the composite films showed that ZnO exhibited a suitable buffer layer that could block holes movement throughout the heterojunction of ITO/ZnO. The enhancement in the fill factor (FF) of the buffer-OSC (BOSC) is attributed to the presence of nanoheterojunctions of ZnO/PCBM and ZnO/ITO. For the normal temperature, the increase of the open-circuit potential and short-circuit current resulted in an overall increase of the energy conversion efficiency. Comparing to OSCs without buffer layer (WOSC), the laminar structure of ITO/ZnO/P3HT/PCBM/Li/Al cells possess a much larger photovoltaic energy conversion efficiency, namely 2.12% (for BOSC) compared to 1.75% (for WOSC).