During the 308 nm laser-driven photochemical synthesis of Cu particles from bis(tert-butylacetoacetato)copper, gas-phase photogenerated intermediates are identified by luminescence and time-of-flight mass spectroscopies. Pure Cu deposits are obtained as homogeneous, granular 200 nm particles. In the gas phase, luminescent photoproducts are observed and atomic Cu, Cut, and dissociated ligand are identified spectroscopically. In addition, mass spectroscopy identifies Cu atoms, the dissociated ligand, a monoligated complex, and fragments of the ligands. The implications of the photofragmentation that produces copper atoms and dimers for the laser-assisted production of the Cu deposits are discussed.