Crystalline ZnSe nanowires have been grown by pulsed-laser deposition on catalyst-coated substrates. On 300-400 °C catalyst-coated silicon (100) substrates, the crystalline ZnSe nanowires can be grown densely with the middle diameters about 40 nm, and the length about 400 nm . The as-grown nanowires were well crystalline and base-grown. They have potential applications in solar cell based on polymer/inorganic hybrid system for their properties of good electron-conductance and high ratio surface area. Based on the ZnSe nanowires cathode, a five-layer composite structure of polymer/inorganic hybrid solar cell has been designed. Before the growth of nanowires, a silver layer with a thickness of about 100 nm was deposited on the Si substrate as the back electrode and catalyst layer by the method of PLD. Then ZnSe nanowires were deposited on the Ag-coated substrate. Subsequently, poly (3-hexylthiophene) (P3HT) and PEDOT: PSS were spin-coated on the ZnSe nanowires. After that, a layer of Clevios PH1000 was also spin-coated on the composite sample as front electrode. At last, the solar cell was encapsulated with epoxy resin. Short circuit current about 0.44mA has been tentatively observed in this complex system.