Heavy oils in sedimentary basins are commonly related to biodegradation and water washing, and thermal degradation of sulfur-rich kerogen at an early hydrocarbon generation stage. However, the potential for overpressure release to form heavy oil has been seldom considered and rarely demonstrated. Paragenetic sequences of diagenetic and oil charge events, pressure-temperature-composition (P-T-x) evolutionary history reconstruction, and molecular geochemical data from a single generation of oil inclusions reveal that heavy shale oil in the PS18–1 well in the Dongpu Depression, Bohai Bay Basin, China, was neither a product of biodegradation nor due to early oil generation during kerogen maturation. Instead, the precipitation and retention of polar compounds of a previously charged, higher-maturity oil from deeper source rocks, induced by intense pressure reduction during basin uplift, represent the most likely mechanism for the formation of the heavy oil. The precipitation of polar compounds during primary and secondary migration due to intense pressure release may be an important mechanism for explaining compositional fractionation effects in the expelled petroleum fluids in source rocks, bitumen, and heavy oil distributions in unconventional shale systems, and deep non-biodegraded heavy oils. This mechanism has wider implications for understanding the hydrocarbon distribution in overpressured basins.