The accumulation of dissociated charge carriers plays an important role in reducing the loss occurring in organic solar cells. We find from light-assisted capacitance measurements that the charge accumulation inevitably occurred at the electrode and photovoltaic layer interface for bulk-heterojunction ITO/PEDOT:PSS/P3HT:PCBM/Ca/Al solar cells. Our results indicate, for the first time through impedance measurements, that the charge accumulation exists at the anode side of the device, and more importantly, we successfully identify the type of charge accumulated. Further study shows that the charge accumulation can significantly affect open circuit voltage and short circuit current. As a result, our experimental results from light assisted capacitance measurements provide a new understanding of the loss in open-circuit voltage and short-circuit photocurrent based on charge accumulation. Clearly, controlling charge accumulation presents a new mechanism to improve the photovoltaic performance of organic solar cells.