Assam coal was subjected to solvent extraction studies using 40 solvents belonging to different class, group and functionality. Boiling point of a solvent was found to have no relation with extractability of coal at atmospheric pressure, excepting within the same class, group and functionality of solvents. Boiling point should not be used for classifying the coal extractability, rather chemical nature of solvent should be used. Cetene (high boiling α-olefin), anthracene oil, liquid paraffin (through thermochemical dissociative extraction) and ethylenediaraine (simple extraction) were found to give good extraction yields from Assam coal. Successive extraction of coal was possible only using anthracene oil or ethylenediaraine. Chemical interaction of these solvents with coal which renders the enhanced amount of coal extractable through stepwise extractions has been discussed. Mechanism and molecular dynamics of solvent extraction of coal in AO, α-olefins etc. has been explained. This is a novel finding in coal chemistry. Stepwise extraction could cut short the total extraction time in anthracene oil. Anthracene oil and high boiling α-olefins extractions result in molecular fluidization of coal macromolecules under ambient pressure. Successive extractions of coal in low boiling solvents ( < 250°C) did not modify on the highest extraction yield of coal in the solvent used in the sequence, whereas in case of successuve chemical dissociative extractions it did.