The compound purificant of external refining of molten steel and production method pertains to the field of smelting ferroalloy, in particular to the purificant dislodging impurity of molten steel and the purificant production method in external refining. The purificant comprises graphite, ferrosilicon, calcium-silicon and bauxite, according to the percentage of weight, is composed of the following components: the carbon content is from 18 per cent to 32 percent, the content of silicon is from 15 percent to 26 percent, the content of iron is from 3 percent to 8 percent, the content of calcium is from 3 percent to 10 percent, the content of aluminum oxide is from 26 percent to 38 percent, the content of water is less than or equal to 0.75 percent, and the remainder is the impurity and adhesion agent. The method producing the compound purificant of molten steel includes these steps of matching material, crashing, mixing, grain-making, drying, checking, piling and bagging, the purificant becomes graininess, and the grain size ranges from 3 mm to 30 mm. The method has the advantages of the extensive material, the convenient machining, the safety and reliability in production, storage and use, the strong capability of purifying molten steel, the low oxygen content of molten steel, promoting slag foaming, favorable submerged-arc operating in fining furnace, improving the thermal efficiency and the ladle age, the excellent effect of desulfurize, improving the recycle rate of manganese and silicon, saving the use of alloy.