The study aims at coal desulphurization prior to its combustion to reduce the environmental hazards. The process of desulphurization was performed by using microwave-assisted technology in alkaline medium. Response surface methodology (RSM) was employed for the optimization of the removal of sulfur from coal samples by microwave treatment in order to study the interactive and simple effects of operational variables. The parameters, that is, coal particle size, power of microwave, and time of irradiation, were examined. Precipitation method with barium chloride was used for the estimation of sulfur removal. Samples of coal were ground into different particle sizes and then slurries of coal were made in aqueous media and finally irradiated with microwaves in the presence of KOH medium. The measured response was sulfur reduction up to 60%. Time of irradiation and power of microwave have significant effect on desulphurization of coal.