Trifluoromethanesulfonic acid supported on attapulgite powder (TFMSA/AP) and Mg-2 Si/gamma-Al2O3 were facilely prepared by impregnating TFMSA onto AP and Mg-2 Si onto gamma-Al2O3. The extraction residue from Yiwu lignite (YL (ER)) was subjected to non-catalytic hydroconversion (NCHC) and catalytic hydroconversion (CHC) over TFMSA/AP and Mg-2 Sity-Al2O3, respectively. Detailed molecular compositions of the soluble portions from the NCHC (SPNCHC) and CHC over TFMSA/AP (SPCHC-A) and Mg2Si/gamma-A1(2)O(3) (SPCHC-A ) were characterized with a gas chromatograph/mass spectrometer. As a result, the yields of SP oic A and SP oic B are 19.6% and 17.5%, respectively, which are much higher than that of SP (NCHC) (1.04%), suggesting that both TFMSA/AP and Mg-2 Si/gamma-Al2O3 show excellent activity for the CHC of YL (ER). Arenes and arenols are predominant in SPCHC-A and SPCHC-B, respectively, while large amounts of alkanoates were detected in SP NcHc. The results indicate that TFMSA/AP effectively catalyzes the cleavage of C-ar-C(alk )and C-alk-O bridged bonds (BBs) in YL (ER) , while Mg2Si/gamma-Al(2)O(3 )significantly promotes the cleavage of C-O BBs in YL ER. Di(1-naphthyl)methane, 1-methylnaphthalene, oxydibenzene, and benzyloxybenzene were used as coal-related model compounds (CRMCs) for the CHC to further explore the catalysis of TFMSA/AP and Mg2Si/gamma-Al(2)O3. The results show that TFMSA/AP not only releases mobile H(+)but also heterolytically splits H-2 to form an immobile H- and a mobile H+, leading to the cleavage of C-ar-C(alk )and C-alk-O BBs in the CRMCs. In contrast, Mg2Si/gamma-Al(2)O3 facilitates heterolytically splitting H-2 to an immobile H- and a mobile H-, resulting in the cleavage of C-O BBs in the CRMCs.