The composition and properties of heavy toluene soluble fraction (HTSF) from hydro-coprocessing of Yanzhou coal (YZc) and catalytic cracking slurry oil (CCSO) were studied by using thin layer chromatography (TLC), nuclear magnetic resonance (1H NMR) and gel permeation chromatography (GPC). The effects of reaction conditions on TLC composition, structural parameters and mean relative molecular mass of HTSF were investigated. The result showed that the group composition of HTSF was similar to commercial high grade paving asphalt and HTSF could be used to make high grade paving asphalt. With the increase of temperature, the mean relative molecular mass of HTSF decreased, and relative molecular mass distribution narrowed, meanwhile, the aromaticity increased and the average carbon number per alkyl side chain decreased.