Organic photovoltaic device comprises a first electrode, a first carrier transfer later, an active layer, a second carrier transfer layer and a second electrode. The first electrode is a transparent electrode. The active layer includes at least one electron donor, a first electron acceptor, and a second electron acceptor. Wherein, the electron donor is an organic polymer. The first electron acceptor is a crystalline material, and the self-molecule stacking distance of the first electron acceptor is less than 4 Å. The second electron acceptor is a crystal destruction material, and the second electron acceptor includes a fullerene derivative. The organic photovoltaic device of the present invention not only has a controllable morphology formation but also can enhance fill factor and improve power conversion efficiency.