Gas phase 308 and 350-370 nm photolysis of bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)copper(II), Cu(hfac)(2), produces CuF as well as copper atoms and dimers, These metal-containing fragments, identified by luminescence spectroscopy, are studied under a variety of gas phase conditions ranging from 1 bar in a static chamber to 10(-4) mbar in a collision-free molecular beam. Copper atom and dimer luminescence is observed at the higher pressures, whereas at low pressures (total pressure no greater than the vapor pressure of the sample) exclusively CuF emission is observed. The a, A (omega = 0, 1, 2), B, and C excited states at 681.0, 567.6, and 505.1, and 491.7 nm are observed, The (3) Pi(0)(-) component of the A state is observed for the first time. The CuF luminescence obeys a quadratic power law with 308 nm excitation. The partitioning of excess energy into fragment degrees of freedom is determined from the intensities of the emission lines. The vibrational and rotational temperatures of the CuF fragment are in excess of 1700 K. Mechanisms of CuF formation, comparisons with the free ligand and with other volatile copper complexes, and the implications for laser-assisted chemical vapor deposition are discussed.