An oil-soluble molybdenum catalyst was synthesized by a simple and novel method and studied for hydrogenation in coal-oil co-processing. The catalyst was characterized by infrared spectrum (IR), thermogravimetry (TG), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The morphology and crystal structure of catalyst was characterized with scanning electron microscope (SEM) and high resolution transmission electron microscopy (HRTEM). The catalyst can be considered as a precursor that can be converted into active MoS2 components through thermal decomposition and sulfidation. The hydrogenation experiment was carried out by the model reactants of tetradecane and 2-methylnaphthalene with a change of reaction (405℃-445℃) temperature and concentrations of molybdenum catalyst (Mo conc. 0.6-10 mg/g), and results showed that the delightly hydrogenation function of catalyst is to improve the saturation of aromatic ring. The most abundant stacking numbers of decomposed catalyst were 2 and 3, accounting for 53% of all catalyst microcrystalline units. The rapid hydrogenation stage and the significant decrease of feed heavy fraction in co-processing experiment provided the evidence that the hydrogenation performance of the synthesized catalyst is remarkable in coal-oil co-processing.