The effects of the Zr/Ti ratio on the electrical properties of lead zirconate titanate (PZT) thick films prepared by the aerosol deposition (AD) process were investigated to optimize the electrical properties of the thick film. The Zr/Ti ratio was varied among 45/55, 52/48, and 60/40, and the post-annealing temperature was varied from 500 to 900 °C. Microscopic examination of the as-deposited films revealed crack-free and dense microstructures with a thickness of 10 μm. The annealed films showed markedly improved electrical properties in comparison with the as-deposited films with increasing post-annealing temperature. With increasing Zr/Ti ratio, the remnant polarization and coercive field decreased. The dielectric constant and piezoelectric coefficient, d33, were highest for the PZT 52/48 film. This film annealed at 900 °C exhibited the best overall combination of electrical properties, with a dielectric constant, remnant polarization, and piezoelectric coefficient of 1320, 31.1 μC/cm2, and 150 pC/N, respectively.