Photodissociation of trimethylaluminum [Al(CH3)3] adsorbed on a silica (SiO2) substrate at 110 K has been studied by multiphoton ionization time-of-flight mass spectrometry. Translational energy distributions of aluminum and AlCH3 fragments can be fitted with a composition of two Maxwell–Boltzmann distributions. The two components are attributed to different environments of photodissociating parent molecules in the multilayer.