Pure gold films are deposited on germanium, silicon, silicon dioxide, and quartz by photolyzing (CH3)(2)Au-(hexafluorbacetylacetonate) in the gas phase. Shiny gold films are deposited at low incident fluences (<5 mJ/cm(2)), whereas higher fluences yield dull brown deposits. The effects of the fluence and the repetition rate of the pulsed laser on the morphology of the deposited film are studied by using SEM. The film quality is analyzed by using XPS and Auger spectroscopic methods. No detectable carbon is found in either the gold or brown films, indicating that both ate pure gold with different surface morphologies. Luminescence in the gas phase is observed under the conditions used for the photodeposition. The emission spectrum, containing two bands having well-resolved vibronic fine structure, originates from dimeric gold, Au-2. The spectroscopic identification of ligand-free gold indicates that there is a gas-phase photochemical component in the deposition process. Deposition mechanisms, including both a surface component and a gas-phase component, are discussed.