In this article, to form a structure-controlled interface, carbon fiber (CF) surfaces were first activated by plasma technique and then hydroxylated by LiAlH4 treatment, and then were reacted with a suit of silane-coupling agents terminated with desired functional groups to form thin films, which further reacted with polyimide (PI) resin to generate a strong adhesion interface. The morphology, structure, and composition of CF surfaces before and after treatment were investigated by atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS), respectively. The results of FTIR and XPS analysis showed that silane-coupling agents were successfully chemisorbed onto the CF surfaces by the hydrolysis and condensation reactions. The interfacial shear strength of the CF/PI microcomposites was evaluated by the microbond technique. The results showed that the types of the interfacial functional groups, especially the vinyl end groups in vinyltriethoxysilane (VS), which can react with PI resin, had very significant influence on the improvement of the interfacial adhesion properties of composites. (c) 2007 Wiley Periodicals, Inc.