Enhanced performance of an inverted-type polymer solar cell is reported by controlling the surface energy of a zinc oxide (ZnO) buffer layer, on which a photoactive layer composed of a polymer:fullerene-derivative bulk heterojunction is formed. With the approach based on a mixed self-assembled monolayer, the surface energy of the ZnO buffer layer can be controlled between 40 mN m−1 and 70 mN m−1 with negligible changes in its work function. For the given range of surface energy the power conversion efficiency increases from 3.27% to 3.70% through enhanced photocurrents. The optimized morphology obtained by surface energy control results in the enhanced photocurrent and transmission electron microscopy analysis verifies the correlation between the surface energy and the phase morphology of the bulk heterojunction. These results demonstrate that surface energy control is an effective method for further improving the performance of polymer solar cells, with potentially important implications for other organic devices containing an interface between a blended organic active layer and a buffer or an electrode layer.