Experiments of the photodissociation of tetramethyltin by synchrotron radiation and the epitaxial atomic layer growth of diamond structured α‐Sn films are reported. We used surface sensitive core and valence band photoemission spectroscopy to study the temperature dependence of the condensation and desorption behavior of tetramethyltin on CdTe(100). A quantitative analysis of the deposition and photodissociation of tetramethyltin including the work function change and the evolution of the substrate Te 4dand overlayer Sn 4dintensities during the overlayer deposition suggests that individual monolayers can be grown by the technique of synchrotron radiation assisted metal organic layer epitaxy. The photofragmentation process does not cause a significant carbon build up in the overlayer film. The photodissociated hydrocarbons seem to recombine and desorb from the surface.