The invention discloses a preparation method of a calcium molybdate / molybdenum disulfide composite luminescent material. The preparation method specifically comprises the following steps: dissolving 0.85g of sodium molybdate into 30mL of water, stirring for 5 minutes so as to generate a sodium molybdate water solution, pouring the sodium molybdate water solution into a polytetrafluoroethylene liner, soaking two egg shells into water, taking off inner membranes attached to the egg shells, and putting the inner membranes into the sodium molybdate water solution; and putting the polytetrafluoroethylene liner into a reaction kettle, sealing the reaction kettle, putting the reaction kettle into a drying oven to react at 160-240 DEG C for 24 hours, taking out the product, cleaning the product to be neutral by virtue of deionized water and absolute ethanol, and drying at 40 DEG C for 6-48 hours, so as to obtain the calcium molybdate / molybdenum disulfide composite luminescent material. The composite luminescent material can emit blue light and green light under an ultraviolet excitation condition. The simultaneous emission of the blue light and the green light is realized by virtue of compounding of molybdenum disulfide for the first time on the premise that a rare earth element is not introduced, and a synthetic process is relatively simple and low in cost.