We report the first observation of piezotronic effect on the output voltage of a flexible heterojunction solar cell. The solar cell was fabricated by contacting poly(3-hexylthiophene) (P3HT) with one end of a ZnO micro/nanowire to form a p-n heterojunction on a flexible polystyrene (PS) substrate. The open-circuit voltage V(oc) of the solar cell was characterized by tuning the strain-induced polarization charges at the interface between ZnO and P3HT. The experimental data were understood based on the modification of the band structure at the p-n junction by the piezopotential, which is referred as a result of the piezotronic effect. This study not only provides an in-depth understanding about the effect but also is useful for maximizing the output of a solar cell using wurtzite structured materials.