The authors have studied the characteristics of tungsten (W) and carbon (C) thin films, and W/C multilayers prepared by ArF excimer‐laser‐induced chemical vapor deposition using tungsten hexafluoride and benzene gases. Amorphous W and C films with very smooth surfaces were obtained at substrate temperatures of 100–200 °C and 100–300 °C, respectively. In small‐angle x‐ray scattering measurements for the multilayers deposited at 200 °C, a first order of multilayer reflections were clearly observed. Furthermore, Auger electron spectroscopy showed that W and C layers in the multilayers were periodically deposited.