Acetylene carbon black and polyvinylidene fluoride (PVDF) based porous electrodes were fabricated from supercritical carbon dioxide drying method at 10.0-20.0 MPa and 40 degrees C. Their morphologies, porosities and electrical properties were investigated and compared with the electrodes fabricated from a conventional solvent evaporation. Additionally, those electrodes were practically applied in Li-air battery and tested on the discharge charge profile for more than 3 cycles. The results show that the porous carbon electrode from supercritical drying has the porosities higher than 90% which is 1.6 times higher than those from the solvent evaporation. Moreover, the supercritical drying pressure affects the porosities and conductivities of the porous carbon electrodes which considered from the mass transfer on the drying and crystallinity variation of PVDF. In the Li-air battery test, it was found the specific electric capacity at the first cycle increases with increment of the porosity.