We determine the thermal ionization energy of the excited state of Ce3+ in a SrHfO3 host by a contactless optical method based on the measurement and analysis of delayed recombination decay following UV excitation. We show the applicability of the method for microcrystalline powder samples. The method provides a consistent value of thermal ionization energy of about 0.25 eV, as previously determined by a ther‐ mally stimulated luminescence (TSL) study after UV illumination. We reveal a low temperature contribution to the delayed recombination signal and address its origin. This contribution indicates a complex interaction of the luminescence center with the host lattice neighborhood and the presence of temperature independent losses of fast scintillation light. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)