One of the priority goals of sustainable socio-economic development for the period up to 2030 is providing food for the planet’s population. This entails an increase in the output of mineral fertilizers and, consequently, an increase in the quantities of solid industrial waste. Phosphogypsum, a by-product of phosphate fertilizer production from apatite ore, is one example of such waste. The problem of solid industrial waste recycling is urgent. The present study examines the process of converting calcium sulfate, in the form of a reagent, and phosphogypsum into a composite material of calcium sulfate/sulfide. An environmentally friendly material, sucrose, is used as a reducing agent. Reduced phosphogypsum (as well as calcium sulfate) luminescence is suggested to be associated with the formation of a CaS/CaSO4 composite material. The synthesized materials are characterized by X-ray phase analysis, X-ray photoelectron spectroscopy, elemental analysis, and calcium sulfide qualitative and quantitative content in the samples. It is shown that in the reduction process at the phase contact point, crystal grids are formed with a significant number of defects, which contributes to the convergence of some of the energy levels of the calcium cation and sulfide anion, facilitating the transitions of electrons from the valence zone to the core zone and the formation of luminescence centers (cross-luminescence). Both samples of reduced phosphogypsum and alkaline earth metal sulfates are found to exhibit luminescence properties under ultraviolet radiation. The data obtained open up broad prospects for the use of solid industrial waste for the synthesis of new materials.