The sol-gel processing route was used to synthesize thin layers of various compositions in the Pb(Zr_xTi₁)O₃ system. Low-temperature crystallization behavior is believed to be influenced by local order and the coordination of the species in the starting precursor structure. The aim of this research was to understand how structure evolves through drying, thermolysis, densification, and crystallization. The observed transformation from molecular level heterogeneity at lower temperatures to intermediate range order, and eventually to the long-range ordered perovskite structure at higher temperatures, was determined by EXAFS spectroscopy.