The invention discloses a coal dressing composite reagent and a preparing method thereof. Raw materials used in the preparing method of the coal dressing composite reagent include, by mass percent, 65% of arene residual liquid, 15% of butanol and octanol residual liquid, 5% of light diesel oil, 1%-5% of an emulsifying agent and 10%-14% of water. The manufacturing method of the coal dressing composite reagent comprises the following steps that the arene residual liquid, the butanol and octanol residual liquid and the light diesel oil are mixed according to a required proportion and put into a reaction kettle with a stirring function, stirring is conducted for 30 min, and mixed oil liquid is formed; and the emulsifying agent and the water are mixed according to a required proportion, a mixed solution of the emulsifying agent and the water is obtained, the mixed solution of the emulsifying agent and the water is added to the obtained mixed oil liquid under the stirring condition at the stirring rate of 100 rmp, and stirring is conducted continuously till the solution is brown. Selectivity of hydrocarbon oil on cleaned coal can be improved through the coal dressing composite reagent, a floatation effect is improved, the floatation cost is saved, in addition, products high in additional value are produced by reasonably utilizing the arene residual liquid, and very good economic benefits and social benefits are achieved; and meanwhile the beneficial effects of facilitating energy saving and emission reducing, improving the economic benefits and the like are achieved.