The objective of this paper is to compare the surface features of two kinds of nano-porous activated carbon fiber (NPACF) treated with potassium and the variation of their properties by phosphoric acid pre-treatment. X-ray diffraction (XRD) patterns indicate that NPACF containing potassium species show better performance for potassium and potassium salts by pre-treatment with phosphoric acid. In order to present the causes of the differences in surface properties and specific surface area after the samples were treated with phosphoric acid, pore structure and surface morphology are investigated by adsorption analysis and SEM. For the chemical composition microanalysis for potassium loading of the NPACF pre-treated with phosphoric acid, samples were analyzed by EDX. Finally, the type and quality of oxygen groups are determined from the method proposed by Boehm.