Thin film electro-optic and non-linear optical materials are of interest for applications in high-speed integrated optical devices. Materials of the system Pb1-x/100Lax/100(Zry/100Ti1-y/100)1-x/400O3 or PLZT x/y/(100-y) are attractive since they can be integrated into Si and GaAs substrates using suitable deposition techniques. In this investigation we examine the structural properties of r.f. magnetron sputter-deposited PLZT using X-ray absorption near-edge spectroscopy (XANES). For XANES analysis, four samples were selected : (1) a highly oriented PLZT 28/0/100 film of almost-equal-to 4500 angstrom deposited on SiO2; (2) a highly oriented PLZT 28/0/100 film of almost-equal-to 4500 angstrom deposited on a 2 mum SiO2 buffer layer over a Si(100) substrate; (3) a highly oriented PLZT 28/0/100 film of almost-equal-to 4500 angstrom deposited on Al2O3 (1102); and (4) a commercial ceramic wafer of PLZT 9/65/35. The XANES experiments were performed at the Stanford Synchrotron Radiation Laboratory (SSRL) using electron yield and fluorescence techniques. Data was taken at the Ti K-edge (4966.4 eV) and compared to reference spectra. Of the reference spectra, the Ti K-edge spectra of the PLZT most closely resemble perovskite (SrTiO3). The surface and bulk thin film are similar and all the 28/0/100 spectra resemble the spectra of 9/65/35, indicating similar cubic perovskite structures for these materials.