In order to achieve the resourceful, large-scale and high-value utilization of bulk industrial solid wastes such as flue gas desulfurization gypsum (FGDG), fly ash (FA) and ground blast furnace slag (GGBS), and to reduce the dosage of cementitious materials, orthogonal experimental methods were used to prepare composite cementitious materials based on the principle of synergistic coupling and reconstruction of multi-solid wastes. Through the method of extreme difference and ANOVA, the influence law of different factor levels on the performance of the cementitious materials was studied, and the maximum compressive strength of cementitious materials was reached when the ordinary Portland cement (OPC) dosage was 20%, the FGDG dosage was 56%, the FA dosage was 19.2% and the slag dosage was 4.8%, and the W/B was 0.55. The hydration products and microscopic morphology of the cementitious materials were analyzed by means of XRD, SEM and MIP techniques, so as to elucidate the complex synergistic hydration mechanism, and then to determine the more optimal group distribution ratio. The results show that the hydration reaction between FGDG and OPC can be synergistic with each other, and C-A-H further generates AFt under the action of SO₄²−, and at the same time, it plays the role of alkali-salt joint excitation for FA–GGBS, generates a large amount of cementitious materials, fills up the pores of the gypsum crystal structure, and forms a dense microstructure.