We present an efficient hybrid solar cell based on poly (3,4-ethylene-dioxythiophene):polystyrenesulfonate and planar Si with (100) and (111) orientations. The effect of Si surface native oxide on cell performance is studied. Compared to cell with hydrogen-terminated Si surface, the cell with oxygen-terminated Si surface reveals a 530-fold increase in power conversion efficiency (PCE) from 0.02% to 10.6%. The formation of SiOx-Si bonds poses a net positive surface dipole which leads to a favorable band alignment for charge separation. However, thicker oxide degrades cell performance due to higher series resistance. This study demonstrates the highest PCE reported to-date in this field.