In this work, the effect of anodic oxidation treatment on Cr(VI) ion adsorption behaviors of activated carbon fibers (ACFs) was investigated. The aqueous solutions of 10 wt% H3PO4 and NH4OH were used for acidic and basic electrolytes, respectively. Surface characteristics and textural properties of ACFs were determined by XPS and N2 adsorption at 77 K. The heavy metal adsorption of ACFs was conducted by ICP. As a result, the adsorption amount of the anodized ACFs was improved in order of B-ACFs 〉 A-ACFs 〉 pristine-ACFs. In case of the anodized treated ACFs, the specific surface area was decreased due to the pore blocking or pore destroying by acidic electrolyte. However, the anodic oxidation led to an increase of the Cr(VI) adsorption, which can be attributed to an increase of oxygen-containing functional groups, such as, carboxylic, lactonic, and phenolic groups. It was clearly found that the Cr(VI) adsorption was largely influenced by the surface functional groups, in spite of the reduced specific surface area of the ACFs.