Polyimide thin films were prepared by vapor-deposition polymerization. Naphthalene carboxylic dianhydride (NTCDA) was coevaporated with either diamino naphthalene (DAN) or diamino benzophenone (DAB). Coevaporation of dianhydride and diamines yielded thin films of polyamic acids. A polyimide thin film was obtained by annealing the codeposited film of NTCDA-DAB. On the other hand, the codeposited film of NTCDA-DAN was not imidized by annealing. In both cases, chemical structures of the products were not largely influenced by the molar ratio of depositing monomers if sufficient amount of diamine molecules are supplied in the coevaporation process.