The theoretical basis of charge transfer coupling only to the harmonic modes of lattice vibration does not satisfactorily explain the observed uranyl luminescence spectrum and excited state dynamics. Anomalous hot bands at the low-energy side of the origin lines of the charge transfer transition lack a satisfied interpretation. Anharmonicities induced by the interplay of charge transfer and lattice displacement may play an important role in uranyl systems with regard to both spectroscopic properties and excited state dynamics. We have used an anharmonic charge transfer vibronic exciton (CTVE) model to provide a consistent explanation to the anomalous uranyl luminescence spectra. (C) 2007 Elsevier B.V. All rights reserved.