Thin films of transition-metal carbides ZrC, HfC, and TiC were deposited by pulsed-laser deposition under vacuum. The surface chemistry of the films was characterized with ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy, and Auger electron spectroscopy in situ. X-ray diffraction was used to characterize the film structure. TiC was shown to be nearly stoichiometric and polycrystalline. The TiC was applied to a vertically aligned carbon nanotube sample and characterized by field emission. Field-emission results showed enhanced current and current density at a film thickness, 5 nm, not previously reported in the literature. Emission from TiC films was also shown to be less affected by adsorbates during field emission. Pulsed-laser deposition of TiC offers a distinct advantage over other techniques in that high-quality films can be obtained under ultrahigh vacuum conditions without the use of a reactive background gas or excessively high annealing temperatures. The application of TiC by pulsed-laser deposition as a cathode coating shows potential for integration into a fabrication process.