A multilayered structure consisting of ferroelectric Pb(Zr,Ti)O3 (PZT) film is deposited by sputtering on the crystalline silicon p-n junction without any buffer layer. The photovoltaic output of the p-n junction is greatly enhanced due to the usage of In2O3:Sn(ITO)/PZT as top surface passivation layers. The short circuit current and photoelectric conversion efficiency of the p-n junction with ITO/PZT ferroelectric films increase about four and six times, respectively, compared with those without any passivation layers. Improvement in the passivated device is mainly attributed to the built-in field at the ITO/PZT interface.