We demonstrate engineering the photocharge generation efficiency of nanoparticles on the nanometer scale by using a type-II band-gap structure. Compared to bare CdSe cores, the dispersion of type-II core/shell nanoparticles in photorefractive polymer led to an average 100% increase in photocurrents. An improvement to the refractive-index construction time, and a near 100% enhancement to the two beam coupling net-gain coefficients and four-wave mixing internal diffraction efficiencies have been achieved at moderate biases.