In this work, the catalytic reduction of NO over activated carbon fibers (ACFs)/Ag prepared by nanoscaled Ag electroplating has been studied. It is observed that silver content on ACF surfaces increases with increasing the plating time. However, a decrease of adsorption properties, including BET’s specific surface areas and total pore volumes, in increasing the plating time is observed within the range of well-developed micropore structures. As the experimental results, the net heat of adsorption of the ACFs/Ag samples is largely influenced on the amount of silver metal, and the catalytic ability for NO removal over ACFs/Ag samples is improved in the presence of silver on the ACFs. However, the adsorption properties of the excessively silver loaded samples are significantly reduced, resulting in the decrease of the removal efficiency. Therefore, the NO removal is largely depended on silver content on ACFs, together with the results of adsorption properties of the ACFs.