Molecular polarization of ferroelectric poly(vinylidene fluoride) (PVDF) is manipulated at the nanometer scale in order to influence the local electronic structure and reactivity at the surface. A direct current voltage, applied through a conductive scanning probe tip, is used to pattern ferroelectric domains in a PVDF thin film, and the polarization direction of these domains influences the kinetics of electron exchange at the surface. By means of a surface photoreduction reaction, which occurs in a metal ion solution under ultraviolet irradiation, metal nanoparticles are deposited in predetermined configurations on polymer surfaces. The photoexcited carriers are generated from defect states within the energy gap of the material, and these gap states are found not only at the interface but throughout the bulk polymer. This represents the first demonstration of ferroelectric nanolithography on an organic substrate and opens the door to applications in organic electronics.