Positron annihilation lifetime spectroscopy measurements identify A- and B-site cation vacancies in ferroelectric perovskite oxides (ABO(3)). Crystal PbTiO3 and ceramic lead zirconium titanate (PZT) were studied and gave consistent values for the lifetime resulting from positron localization at lead vacancies V-Pb. Positron trapping to B-site vacancies was inferred in PZT. Temperature dependent studies showed that the defect specific trapping rate was higher for V-B compared to V-Pb, consistent with the larger negative charge. Doping PZT with Fe increased the fraction positron trapping to V-B compared to V-Pb-type defects.