Industrial wastes, such as phosphogypsum, are characterized by high production and accumulation volumes, and significant pollution. A high-performance, all-solid waste, phosphogypsum-based composite cementitious material (PCCM) was developed by using a hybrid ball milling method and thermal activation to stimulate various industrial wastes. Optimization of rationing was analyzed using extreme variance, standard variance, and multiple regression models. The macro-engineering parameters of PCCM were evaluated through flexural and compressive tests. The mineralogical composition, functional groups, micro-morphology, and molecular structure of PCCM were examined through micro-testing. When the mass ratio of Ball milled calcined phosphogypsum (BCPG) to granulated blast furnace slag (GGBS) is 1.2:1, with a 4 % addition of calcium oxide and a water-cement ratio of 0.4, the 28-day flexural and compressive strengths, as well as the softening coefficients, of PCCM can reach 7.27 MPa, 40.1 MPa, and 0.922, respectively, closely matching the performance of C42.5 cement. Under the synergistic effects of the hydration reaction and an alkaline environment, the CaSO4 in the PCCM system hydrated and crystallized to produce gypsum-phase crystals, enhancing early strength properties by 60–174 %. As hydration continued, SO42- reacted with silicon and aluminum oxides, prompting secondary hydration of GGBS, and increasing AFt and C-(A)-S-H in the system. This research offers a new approach for the co-disposal and resource utilization of various solid wastes while identifying a cementitious material that can replace traditional cement in practical engineering applications.