The photofragmentation and photoionization of the lanthanide-based chemical vapor deposition precursor, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)Ln (III) or Ln(thd)3 was probed using laser photoionization time-of-flight mass spectrometry and a pulsed supersonic expansion source. Depending upon conditions, the mass spectrum was dominated by the parent ion and fragments representing loss of intact ligands or, instead was dominated by bare metal ion and the corresponding metal oxide. For Pr(thd)3 the aquo adduct was strongly represented. The dependence of the fragmentation pattern on the laser wavelength and power and on the identity of the metal ion will be discussed. In particular, the relationship between the observed fragmentation pattern and the electronic structure of the complex and the implications for laser assisted chemical vapor deposition will be explored.