The invention relates to a preparation method of high-calcium aluminum residue balls. The preparation method comprises the steps of 1, soaking bauxite in hydrochloric acid for 3-5 hours; 2, conductingsolid-liquid separation on substances formed in step 1, and introducing ammonia gas into obtained liquid till PH of a solution reaches 7-7.5; 3, drying the liquid obtained in step 2 for 2-3 hours inthe environment with the air pressure being 3.5-4.5 kPa and the temperature being 25-35 DEG C, so that NH4Cl crystals are obtained; 4, adding limestone to solid obtained in step 2, and after the materials are stirred uniformly, conducting calcination for 2-2.5 hours at the temperature of 890-920 DEG C, wherein the weight ratio of the bauxite to the limestone is 1: (0.95-1); 5, adding coke powder and barium carbonate to solid obtained in step 4, and fully stirring the materials to be uniform, wherein the weight ratio of the bauxite to the coke powder is 1: (0.12-0.145), and the weight ratio ofthe bauxite to the barium carbonate is 1: (0.015-0.02); 6, heating materials formed in step 5 to 1500-1550 DEG C in a vacuum environment, conducting calcination for 1.5-2 hours, and conducting negative pressure extraction in the calcination process; and 7, pouring molten materials obtained in step 6 into a mold, and delivering the materials out of the mold after the materials are cooled. By meansof the preparation process, no SOX is generated; and the obtained high-calcium aluminum residue balls are stable in surface and good in outward appearance.