MoS2 was used as an efficient catalyst for hydropyrolysis (Hypy) of three samples of sedimentary organic matter with different maturities. Through comparison with Soxhlet extraction (SE),it was found that MoS2 catalytic Hypy can remarkably promote the yields of total chloroform extracts,saturates, aromatics, hopanes and steranes. In addition, the difference of biomarker parameters indicated that isomerization of covalently-bound biomarkers is much more difficult than their free counterparts.Meanwhile, the high conversion of total organic carbon (TOC) in MoS2 catalytic Hypy of organic matter proved that the presence of dispersed molybdenum sulfide accelerated the breaking of C-C bonds and the release of hydrocarbons. To address the catalytic mechanism, a series of control experiments based on free Hypy and catalytic Hypy were conducted. The results showed that the calculated atomic ratio of carbon conversion/hydrogen conversion for catalytic Hypy was much larger than the presumed value of 1/2, indicating that intensive hydrogenation took place and significantly influenced the distribution of liquid products. Analysis of stable hydrogen isotope data, infrared spectra and m/z 83 ion chromatograph of the saturate fraction further confirmed this hypothesis. The difference of S content changing (△S) between catalyst-free Hypy and catalytic Hypy, and the thermal characteristics of the catalyst, indicated that active H2S was definitely generated and it probably initiated free radical reactions in the early stage of hydropyrolysis of organic matter.