Deep level transient spectroscopy (DLTS) has been used to investigate trap levels in sol‐gel derived polycrystalline Pb(Zr0.54,Ti0.46)O3 thin films. Metal‐ferroelectric‐metal capacitor structures 2400 and 3000 Å in thickness were fabricated and characterized using a constant voltage DLTS system. Prominent peaks associated with a single trap level were observed in all samples studied. The activation energy was determined to be 267 meV from DLTS spectra Arrhenius plots. Infrared transmission characterization was performed on PbTiO3 thin films also prepared using sol‐gel synthesis. A loss in the transmission at 270±12 meV was observed which we attribute to hole emission from the same trap detected using DLTS.