A thin passivation layer of aluminum oxide was deposited on polyimide by using the combined plasma immersion ion implantation and deposition (PIII&D) and cathodic vacuum arc technique. X-ray photoelectron spectroscopy C 1s spectra showed that the carbonyl bond (C=O) and ether group (C-O-C and C-N-C) presented in pristine polyimide were damaged by implantation of aluminum ions and deposition of an aluminum oxide passivation layer. 0 Is and Al 2p spectra confirmed the formation of a thin aluminum oxide passivation layer. This passivation layer can be implemented in aerospace engineering where polyimide may suffer degradation from fast atomic oxygen in the low-earth-orbit environment. To test the protection of this passivation layer to energetic oxygen ions, a plasma-enhanced chemical vapor deposition system was used to simulate the oxygen-ion irradiation, and the results showed that a higher weight occurred for passivated samples compared to pristine ones. X-ray diffraction showed that Al peaks were presented on the surface region, but no aluminum oxide peak was detected. The authors then concluded that Al clusters were formed in polyimide besides aluminum oxide, which was in an x-ray amorphous state. Furthermore, contact-angle measurements showed a reduced contact angle for passivated polyimide from a pristine value of 78 degrees to 20 degrees by using deionized water. Several discussions have been made on the surface chemical and structural property changes by using the combined PIII&D and cathodic vacuum arc technique.