A structure of photovoltaic cell is provided. The structure of photovoltaic cell includes a substrate, a lower conductive layer, a photovoltaic layer, and an upper conductive layer, the lower conductive layer is disposed at one side of the substrate, the photovoltaic layer is disposed at the other surface of the lower conductive layer, and the upper conductive layer is disposed on the other surface of the photovoltaic layer. An electron transporting layer, a hole transporting layer, and an active layer sandwiched between the electron transporting layer and the hole transporting layer collectively constitute the photovoltaic layer. The electron transporting layer convers a portion of the active layer and the hole transporting layer for blocking the upper conductive layer from electrically connecting to the active layer and the hole transporting layer.