The present invention discloses a photovoltaic device comprising a multilayer structure for generating and transporting charge, wherein the multilayer structure comprises: a substrate; an anode layer; a hole transporting layer; a first nanostructure/conjugated polymer hybrid layer; an network-shaped electron transporting layer matched to the hybrid layer; and a cathode layer. The mentioned electron transporting layer is composed of a plurality of second nanostructures, and the plurality of second nanostructures is staked on each other, so as to form the interconnecting network. Furthermore, this invention also discloses methods for forming the photovoltaic device.