Abstract Residues from the liquefaction of Black Thunder subbituminous and Illinois No. 6 bituminous coals in an autoclave and a bench unit were examined petrographically. Optical microscopy proved valuable for ranking the samples on the basis of overall coal conversion and presence of vitroplast, granular residue and inertinite. It was observed that in the autoclave that runs on Black Thunder coal, K 2 CO 3 was a superior water gas shift reaction catalyst to NaAlO 2 , or a combination of CS 2 and Fe or Mo catalysts. The amount of vitroplast showing vacuoles and cenospheric morphology in the residues was inversely related to the CO conversion, indicating that the mechanism of vitroplast dissolution is linked to the availability of active CO intermediates (e.g. formate ion, HCOO − ). A CO-steam mixture was more effective than syngas or pure H 2 and N 2 in increasing Black Thunder coal conversion, and resulted in greater morphological changes to the coal particles. In contrast, for Illinois No. 6 coal pure H 2 had a greater effect on coal solubilization and overall conversion than pure CO at the same temperature; this was attributed to the absence of carboxylates to react with the formate ions. Higher mesophase and coke contents were detected in some bench unit runs on Black Thunder coal that were operated in counterflow mode. Higher severity, poorer mixing, longer residence time and a reduction in pressure by almost 3.5 MPa are believed to be responsible for the retrogressive reactions forming mesospheres in these cases.