Refractory coatings of TiC and TiB2 have been grown by pulsed laser deposition on Si(100) and on X155 steel at various substrate temperatures ranging from 40°C–650°C. A pulsed KrF excimer laser was used with the deposition chamber at a base pressure of 10−6 mbar. The morphology and structure of the films, studied with scanning electron microscopy (SEM), X-ray diffractometry (XRD) and transmission electron microscopy (TEM) analysis, showed that polycrystalline films with fine morphology of TiC and TiB2 were deposited with grain sizes of 10 nm–70 nm at all substrate temperatures. Shifts in the X-ray diffraction peaks were attributed to the presence of residual stresses in the films, which decreased as the substrate temperature was increased. Finally, the metallic behavior of the coatings was studied by electrical resistivity measurements.