Plasma polymerization of allylamine subsequently after plasma pre-treatment was conducted on the activated carbon fibers (ACFs) for the immobilization of amine groups in the surface of ACFs. The change of structural properties of ACFs with respect to different polymerization conditions was investigated through BET method. The change of surface morphologies of ACFs with respect to different plasma polymerization power was also studied through AFM. It was found that the structural properties such as specific surface area and micropore volume could be optimized under certain plasma deposition conditions. It was reckoned that treatment and deposition showed adverse effect on plasma polymerization, in which the former developed the micro-structures of the ACFs and the latter tended to block the micro pores. The Fourier transform infrared spectroscopy (FTIR) revealed that the poly(allylamine) was successfully immobilized on the surface of ACFs and the amount of the deposited polymer layer was related to the plasma polymerization power. SEM results showed that the plasma deposited polymer layer were small and homogenously distributed. The size and the distribution of particles deposited were closely related to the plasma polymerization power, too.