Pulsed laser ablation in deionized water was successfully employed to synthesize a Y3Al5O12:Ce3+ nanocolloidal suspension. The obtained suspension consisted of a well-dispersed YAG:Ce3+ nanocrystal with a spherical shape and a size ranging from 5 to 25 nm. Blueshift phenomena were found in excitation and emission spectra, which have not been explained by previous crystal-field splitting theory. This Letter focuses on the simple synthetic route of colloidal YAG:Ce3+ nanocrystals via laser ablation in the liquid phase and 5d energy level of Ce3+. A phenomenological model based on the concept of crystal-field theory modified by the covalency contribution is introduced to explain the blueshift phenomena in luminescence. (C) 2008 The Electrochemical Society.