Four types of activated carbon fibers (ACFs) with different specific surface areas (SSA) were used as electrode materials for water desalination using capacitive deionization (CDI). The carbon fibers were characterized by scanning electron microscopy and N-2 adsorption at 77 K, and the CDI process was investigated by studying the salt adsorption, charge transfer, and also the charge efficiency of the electric double layers that are formed within the micropores inside the carbon electrodes. It is found that the physical adsorption capacity of NaCl by the ACFs increases with increasing Brunauer-Emmett-Teller (BET) surface area of the fibers. However, the two ACF materials with the highest BET surface area have the lowest electrosorptive capability. Experiments indicate that the charge efficiency of the double layers is a key property of the ACF-based electrodes because the ACF material which has the maximum charge efficiency also shows the highest salt adsorption capacity for CDI.