The production of ash-free coal as a clean fuel for high temperature fuel cell was investigated. The ash-free coal was made from a bituminous coal. It was prepared by solvent extraction using a microwave. The solvent-to-coal ratio and microwave irradiation time of raw coal were parameters for the extraction yield. The microwave method showed merits in terms of faster extraction and higher extraction yield than conventional heating methods. In addition, gasification behaviors of the ash-free coal were investigated by gas chromatography. Contrary to carbon, ash-free coal showed hydrogen as a dominant gas species in its gasification and did not require carbonate catalyst. The electrical conductivity of ash-free coal was found very low close to zero.