Optical excitations for trivalent platinum (5d7, t6e) and trivalent Pb (6s1) ions in lead titanate single crystals have been observed for the first time by electron paramagnetic resonance (EPR). The g and hyperfine coupling, A, tensors of Pt+3 defects were found to be axial: gil∥ = 1.938, g⊥ = 2.478, A∥ = 0.0164 cm−1, and A⊥ = 0.0324 cm−1. Analysis of the EPR spectra by crystal field theory indicates that the Pt+3 ions are in tetragonally distorted (elongated) octahedral sites, strongly suggesting that they substitute for the central Ti+4 ions in the perovskite lattice. Axially symmetric Fe+3 impurities were also observed in the crystals, and they also appear to substitute for the Ti+4 cation. Identification of Pb+3 in these single crystals further shows that holes trapped at Pb+2 ions are an inherent feature of Pb-based perovskite ferroelectrics.