Aiming to study the pore structure and its impact on shale oil enrichment, a total of nine lacustrine shales (including one immature shale and eight mature shales) from the Qingshankou Formation in the Songliao Basin were subjected to low-pressure gas sorption (LPGS) of CO2 and N2 and mercury intrusion capillary pressure (MICP) measurements. The combination of the LPGS and MICP methods demonstrates that the pore volumes of these shales are mainly associated with mesopores, whereas the micropores and macropores are relatively undeveloped. The correlation between the shale compositions and pore volumes of LPGS suggests that the micropores and mesopores are mainly contributed by illite/smectite mixed layer mineral. On the contrary, we have found that the oil/bitumen and carbonates could occupy the micropores and mesopores, respectively, and reduce these pore volumes significantly. The oil saturation index (OSI) was found to display a positive correlation with the maturity Ro value in the range of 0.37%–1.24%, and this may suggest that the shale-oil content is controlled by hydrocarbon generation. However, the pore structure also exerts a great influence on the shale oil enrichment. We suggested that the porosity of MICP could be considered as an index for appraising the shale-oil potential of a given shale player because there is a good positive correlation between the porosity of MICP and the OSI value. Furthermore, a negative correlation between the micropore volume and the OSI value may imply that the shale oil could be adsorbed in micropores, whereas a good positive correlation between the OSI value and the Hg-retained ratio suggests that shale oil is a kind of residual hydrocarbon, which is closely related with the mesopore volume of these shales.