High volatile bituminous coals were treated in pyrene and in Ashland A-240 pitch at 400 °C for 0.5 h under nitrogen at near-ambient pressure. The solvolytic liquefaction yield was found to depend on the free-swelling index (FSI) of the coals and the solvent used, with yields approaching 80 wt% maf coal at an FSI of 7 in pyrene. It is proposed that A-240 pitch undergoes addition reactions with fragmented coal via radical substitution on aromatic entities, the resulting material being quinoline-soluble and benzene-insoluble. Infrared spectra of liquefied coal in A-240 pitch show the enhanced presence of aliphatic CH 3 groups. It is suggested that the enhanced presence of these groups increases the fluidity of the pitch-coal reacting system, accounting for the notably higher liquefaction yields with pitch than with pyrene.