Lead scandium tantalate (PST) films with a lead-rich composition were deposited at 500°C by RF sputtering on sapphire substrates coated with Pt and were investigated by cross-sectional transmission electron microscopy. The films consisted almost entirely of the perovskite phase. The grains of perovskite PST had a crystallographic orientation almost parallel to that of the underlying Pt. Some elongated voids were observed. The presence of an interfacial phase, with interplanar spacings consistent with a pyrochlore phase, was demonstrated by electron diffraction and dark-field imaging. The crystallographic orientation of this phase is also nearly parallel to that of the Pt. Energy-dispersive X-ray microanalysis showed that the interfacial phase is lead-deficient. The interfacial phase is irregular in thickness. A reduction in the Pb content of the film leads to a thicker interfacial layer. The implications for the mechanism of growth of PST on Pt and for improvement of the film quality are discussed.