ZnO film was prepared on a p-type Si wafer and then annealed at various temperatures in air and vacuum conditions to research the electrical properties and bonding structures during the annealing processes. ZnO film annealed in atmosphere formed a crystal structure owing to the suppression of oxygen vacancies: however, ZnO annealed in vacuum had an amorphous structure after annealing because of the increment of the content of oxygen vacancies. Schottky contact was observed for the ZnO annealed in an air. O 1s spectra with amorphous structure was found to have a value of 529 eV; that with a crystal structure was found to have a value of 531.5 eV. However, it was observed in these results that the correlation between the electronic characteristics and the bonding structures was weak.