This work reports on the structure and properties of the refractory compounds TiC, ZrC, TiB 2, ZrB 2, TiCZrC, TiCTiB 2 and TiCTiB 2 Co. The deposits were prepared by direct evaporation of TiB 2, ZrB 2, ZrC, TiC and cobalt from single and multiple water-cooled copper crucibles using electron beam heating. TiC and ZrC deposits were also prepared by the activated reactive evaporation process. The vapors were condensed on a molybdenum or tantalum substrate at various deposition temperatures ranging from 650 to 1600 °C. The deposition rate was varied from 0.08 to 6 μm min −1 The deposits were characterized by optical microscopy, scanning and transmission electron microscopy, X-ray and electron diffraction and microhardness determinations. With direct evaporation the deposits contained decomposition products in addition to the parent phases. The composition of the deposits was dependent on temperature of deposition, composition of the evaporant billet and to a small extent the rate of deposition. Deposition temperature, rate of deposition and the composition of the deposit influenced the preferred orientation and the microhardness of the deposits. Surface and fracture cross section morphology and microstructure varied with deposition temperature. The data represent an extensive characterization of refractory compound deposits made by high rate physical vapor deposition processes.