The nitrogen adsorption isotherms at 77.69 K were measured for two samples of activated carbon fibers and their microstructures were investigated. Among established isotherm equations, the Dubinin-Radushkevich equation showed the best agreement with the experimental data, while the Langmuir equation showed a large deviation when employed at low relative pressures. The MP method, t-method and αs-method were used to analyze the pore size distribution. The calculated average pore widths and BET (Brunauer-Emmett-Teller) surface areas for the sample A-13 were 0.86 nm and 1 286.60 m2/g, while for the sample A-16, they were 0.82 nm and 1 490.64 m2/g. The sample with larger pore width was more suitable to be used as additive in chemical heat pumps, while the other one could be used as adsorbent in adsorption refrigeration systems.