To enhance the efficient utilization of industrial solid waste and support the low-carbon transition of cementitious materials, this study used steel slag, coal-fired slag, and desulfurization gypsum as the primary raw materials. A high-performance composite cementitious material system was developed based on the synergistic effects of physical activation (mechanical grinding) and chemical activation (alkali stimulation). This study systematically investigates the raw material characteristics, mix proportion optimization, mechanical behavior, and durability of composite cementitious materials through the integration of response surface optimization design and multi-scale analysis methods. The results indicate that the optimal mix proportions of the composite cementitious material are: 37.2% steel slag, 33.2% coal-fired slag, 9.6% desulfurized gypsum, 20% cement, 4% sodium silicate, and 0.1% superplasticizer. At this mix proportion, the measured 28-day average compressive strength of the composite cementitious material was 40.8 MPa, which closely matched the predicted value of 41.2 MPa from the response surface regression model, thereby confirming the model’s accuracy and applicability. The composite cementitious material demonstrated superior volume stability compared to ordinary cement under both water-curing and drying conditions. However, its freeze–thaw resistance and carbonation resistance were lower than those of cement. Therefore, considering these factors comprehensively, the composite cementitious material is recommended for application in road base and subbase layers.