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This paper discusses the effect of the source rock–reservoir assemblage and the assemblage–induced variability in hydrocarbon expulsion and the subsequent molecular composition as well as molecular thermal maturity within a hybrid shale system. The characterization work was conducted on lithofacies and microlamina scales using core samples from the Chang 7 3 sub-member of the Triassic Yanchang Formation in the Ordos Basin, China. Samples were collected from a narrow interval with a depth range of less than 15 m, and the main characterization work was performed by Rock-Eval pyrolysis and GC–MS analysis. The results show that chemical fractionation of preferential expulsion and migration of the saturated fraction exists in the source rock–reservoir assemblages at both the lithofacies and lamina scales. However, the molecular composition behaves differently at the lithofacies and lamina scale's source rock–reservoir assemblages, in which ∑C 21 − /∑C 22+ is higher in lamina scale reservoir but lower in lithofacies scale reservoir. It is assumed that the low-molecular weight n -alkanes also follow molecular fractionation. The lithofacies reservoir has a lower ∑C 21 − /∑C 22+ because of the strong storage capacity of the laminated micro-reservoir within shale, which prevents the newly generated lighter oil from being charged into the lithofacies reservoir. The variation trends of thermal maturity indices Ts/hopane, the relative pregnane content, and TA(I)/TA(I + II) ratios, which have the same chemical basis with ∑C 21 − /∑C 22+ , carry the same maturity signature as ∑C 21 − /∑C 22+. The above profile of the molecular composition and molecular-derived thermal maturity parameters indicate that within the short interval of a shale system where no differences in thermal maturity are expected, chain scission reactions and their derived thermal maturity indicators are very sensitive to source rock and reservoir. In addition, within a shale system, oil is more easily to expel out from the organic-rich lithofacies that are interbedded with organic-lean lithofacies. Oil expulsion may promote both chain cracking of oil and subsequently kerogen decomposition. This may provide geological evidence to explain why the frequent-stacking assemblage of source rock and reservoir lithofacies in a hybrid shale system is an ideal target for shale oil exploration. [ABSTRACT FROM AUTHOR]