Growth dynamics and surface fine structure of ZnO ultrafine particle (UFP) films prepared by de-gas discharge activated reactive evaporation (de-gas discharge) deposition technique were studied. Spectroscopic study was performed with small angle x-ray scattering (SAXS) and surface extended energy loss fine structure (SEELFS). The SAXS probe of the nature of the film surface should lead to a more complete understanding of the mechanism of film forming and growth dynamics. The highly disordered aggregate film can be described as fractal objects with a mass and surface fractal dimension equal to 2.73 and 2.94, respectively. In addition, the SEELFS spectra of ZnO UFP film was obtained and the data were analyzed by fast Fourier transform. The results indicate that the distance between Zn and O of ZnO UFP film is 1.81 Angstrom. Scanning electron microscope and scanning tunneling microscope were used to study the ZnO UFP film.