The ionized cluster beam deposition (ICBD) technique has been employed to fabricate high-purity polyimide (PI) films. The pyromellitic dianhydride (PMDA) and oxydianiline (ODA) were deposited using dual ionized cluster beam (ICB) sources. Fourier transform infrared spectroscopy (FT-IR) and X-ray photoemission spectroscopy (XPS) studies show that the bulk and surface chemical properties are very sensitive to the ICBD conditions such as cluster ion acceleration voltage and ionization voltage. At optimum ICBD conditions, the PI films have a maximum imidization and negligible impurities(∼;1% isoimide) probably due to the high surface migration energy and surface cleaning effect.