Phosphogypsum is a by-product of phosphoric acid production by a wet-process and can be used to prepare adsorption materials to treat Cd(II) in sewage. Its main component is calcium sulfate dihydrate (gypsum). In the present study, incorporation and adsorption of cadmium on gypsum in an aqueous environment have been investigated using dispersion-corrected density functional theory, and the effect of different vacancy defects on the adsorption and doping of Cd on gypsum was also studied. The results show that Cd impurity defects can form more easily in gypsum crystals with Ca vacancy defects. The increase in both calcium vacancy defects and sulfate vacancy defects is beneficial to the incorporation of Cd in calcium sulfate dihydrate. In addition, the calcium vacancy defects on the gypsum surface can promote the adsorption of Cd(II), while sulfate vacancy defects on the gypsum surface inhibit the adsorption of Cd(II). Therefore, increasing the Ca vacancy defects of gypsum will help in improving the adsorption and curing properties of phosphogypsum for cadmium.