Semi-continuous, packed-column supercritical extraction was investigated for the fractionation of a polycyclic aromatic hydrocarbon (PAH) pitch into its constituent oligomers. The starting pitch had been produced by the catalytic polymerization of pure pyrene using AlCl3. Although neat supercritical toluene (T-c=318.6 degrees C; P-c=41.1 bar) was shown to be an effective solvent for the recovery of both monomer and dimer cuts in high purities, higher-oligomer solubilities in toluene are notoriously low. However, the addition of N-methyl-2-pyrrolidone (NMP) as a co-solvent enhanced oligomer solubilities in the extractive, supercritical-solvent phase by a factor of 3, making possible the recovery of trimer and higher oligomers. An unexpected benefit of the use of NMP is that it was found to suppress the condensation reaction between toluene and the pyrene oligomers - apparently by forming a Lewis acid-base complex with the AlC3 catalyst - that can occur in the extraction column at temperatures above 350 degrees C. (C) 2012 Elsevier B.V. All rights reserved.