Objective In order to investigate the feasibility of preparing Zr/C nanometer multilayer self-propagating reaction film by physical vapor deposition technique as well as the structure and reaction process of multilayer film. Methods Scanning electron microscope (SEM), transmission electron microscope (TEM), energy dispersion analysis (EDS), X-ray diffraction method (XRD) and differential scanning calorimetry (DSC) were employed to evaluate film’s microscopic morphology, periodic structure, composition, crystal structure and reaction characteristics. The influence of film’s structural cycle, deposition time, reaction temperature, interlayer structure and other technological parameters on multilayer film structure and property was analyzed. Results The deposition rates of Zr and C were 27 and 11.8 nm/min respectively; Zr(002) and Zr(101) peaks were found in the film, and C existed as amorphous phase. The surface morphology of Zr/C multilayer film showed “cauliflower-like” shape, cross-sectional morphologies of Zr layer and C layer were smooth and clear. TEM showed that there was a sufficient thickness of interface reaction layer at the interfaces of Zr layer and C layer, which indicated diffusion process occurred during deposition. Exothermic reaction was found appearing at 600 ℃ by DSC, but the weight before and after reaction had no evident change. Conclusion The fairly pure Zr/C nanometer multilayer self-propagating reaction film can be prepared by physical vapor deposition. Acute exothermic reaction exists between Zr layer and C layer during self-propagating reaction and ZrC is produced. No other products are formed.