Effect of anthrecene oil, quinoline and liquid paraffin extraction on the swelling of Assam coal has been studied to find out the degree of cross-linking in the pretreated coals, and to assess the molecular effect of the these solvents in the solid mass of coal, on the flexibility of coal macromolecular aggregation and molecular dynamism. Effect of successive extractions using anthracene oil-quinoline-liquid paraffin sequence, on the extraction of volatilizable components i.e. volatile matter (VM) contents and removal of toxic mineral matter contents of Assam coal has been studied. A relation of C % and VM % in coal with extraction yields through this successive extraction of different coals has been suggested. About 50 - 76% of the total VM present in the original coal can be extracted by the successive solvent extractive disintegration of coal, which was more than that through pyrolysis of coal at 600°C. Recovery of VM renders the combustion of residual coal free of pollution. The solvent refined coal is also obtained as a clean fuel. Thus, the process affords the segregation of toxic mineral matter microconstituents. Solvent extraction should be introduced as the essential coal preparation step to remove the premium organic products from coal before firing it in boilers.