In this paper, the influence of Na2CO3 (NC) on the hydfoliquefaction performances of Hongliulin (FILL) coal with an Fe-based catalyst, gamma-FeOOH (FC), under mild conditions was investigated, and the properties of the resulting preasphaltene and asphaltene were examined. Results show that the addition of NC to FC-catalyzed liquefaction significantly promoted coal conversion and oil production and reduced water production under mild conditions, especially at high initial H-2 pressure. The H-2 consumption of mild liquefaction (0.53-1.93%) is much smaller than that of the traditional liquefaction processes, and the addition of NC to FC can enhance H-2 consumption, especially the runs with weak hydrogen donor solvents. The addition order of NC and FC is an important factor which can affect the activity of FC and NC binary catalysts. There exists a prominent synergistic effect between NC and FC in HLL coal hydroliquefaction, and the synergistic effect could be ascribed to the combined promotion actions of NC for the hydrolyzation of abundant oxygen-containing moieties (such as ether bonds and carbonyl groups) in FILL coal and the depolymerization of macromolecular structures of HLL coal.