The aim of this article was to investigate the effects of electron irradiation in ultrahigh vacuum environment on the surface properties of high-performance carbon/bismaleimide (BMI) composites used in aerospace. The changes in surface chemical composition with increasing irradiation fluence were studied by XPS. The evolution of surface morphology and surface roughness were observed by atomic force microscopy (AFM). The mass loss behavior occurring in the surface layer of the composites was examined. The results indicated that the electron irradiation in high vacuum caused rupture of chemical bonds and cross-linking process in the surface layer, thereby leading to the mass loss behavior and the formation of carbonification layer in the surface of the carbon/BMI composites. The changes in the surface chemical composition were determined by a competing effect existing between the rupture of chemical bonds and the cross-linking process at lower irradiation fluence, and by a degradation process only at higher fluence of electron irradiation. The surface morphology was altered and the surface roughness was increased significantly after electron irradiation. The mass loss ratio first increased obviously at lower fluences, and then reached a plateau value of 0.45% beyond 5 × 1015 cm−2 fluence of electron irradiation. Copyright © 2011 John Wiley & Sons, Ltd.