In this paper, using wet chemical solution deposition processes, the (100)-highly oriented LaNiO3 buffer layers were grown on both silicon and platinized silicon wafers and, sequentially, the highly (100)-oriented PbZr1−xTixO3 thin films with various compositions were obtained on them. The misfit elastic strains were found to be critical factors to determine the orientation of PZT thin films, even though the used LaNiO3 buffer layer reduces the lattice mismatch between PZT films and silicon wafers. For the PZT thin films with x=0.5 and 0.6 on the LaNiO3/platinized silicon substrate, the infrared optical constant, ferroelectric, and dielectric properties were characterized and analyzed with relation to the film orientation and the film grain size. It was found that the finite grain size effect here played a key role in determining these optical and electrical properties. With nanoferroelectric thin films, it is the most useful way of controlling both grain size and crystallographic orientation to tune performance of commercial film devices.