In this Letter, we report observation of fragments of the metal-organic complex, Eu(2,2,6,6-tetramethyl-3,5-heptanedionato)(3) resulting from multiphoton ionization of the complex entrained in an Ar molecular beam. Photofragmentation was observed at 532, 355, 266 run, and in the range of 460-466 nm. At each wavelength, the dominant fragments were bare metal ions in multiple oxidation states and ligand fragments. This fragmentation pattern is interpreted as resulting from excitation to ligand-to-metal charge-transfer states in the sequential ligand dissociation steps. Significantly weaker signal from EuO+ and EuOH+ fragments was also observed with photoionization at 266 nm. (C) 2004 Elsevier B.V. All rights reserved.