The resource utilization of phosphogypsum (PG) is the key to promote the green development of the phosphorus chemical industry. The natural environment and public safety are significantly threatened by the enormous volume of PG storage. In this study, Ca and S were successfully recovered from the PG via a multistep precipitation in the NaOH–BaCO 3 system. The alkali solution can be recycled five times, with a first recovery ratio of about 97.9%, and the decomposition ratio of PG remained above 70% after five cycles. In addition, the recovery ratios of Ca and S in PG are 99.9 and 82.5%, respectively. The product of BaSO 4 can be used as a weighting agent for oil and natural gas drilling mud. The BaSO 4 can also be used as wave-absorbing materials, and its reflection loss value reaches 97.8% of the analytical purity BaSO 4. This work provides a new idea for the efficient recycling of Ca and S in PG with an outstanding application prospect.