Selective deposition of charged polystyrene (PS) microspheres from an aqueous solution on domain-patterned lithium niobate is investigated. The selectivity of PS microsphere deposition can be varied by controlling the deposition temperature. Selective decoration of the positive domains (positive polarization surface charges) is achieved at room temperature and is attributed to the electrostatic interaction of the charged nanoparticles and the polarization surface charges of the ferroelectric. In contrast, at elevated temperatures, the particles decorate the negative domains. This process is explained by considering the pyroelectric properties of lithium niobate.