The microstructure and preferred orientations of rapid thermally annealed Pb(Zr0.53, Ti0.47)O3 films, deposited on Pt/Ti/SiO2/Si electrode/substrates by solution-gel spinning, have been investigated using analytical and high-resolution electron microscopy and X-ray diffraction. The temperature of pyrolysis of the PZT filMS was found to influence the preferred orientation of the film: lower temperatures (350-degrees-C) favored a (111) orientation, whereas higher temperatures (420-degrees-C) favored a (100) orientation. Excess Pb was used to control the A-site stoichiometry of the film particularly at the film surface where Pb-deficient crystals could often be observed. The absence of these crystals was shown to be correlated with an improvement in the dielectric response.