The large-scale storage of industrial solid waste can cause serious environmental pollution issues. Utilizing industrial solid waste to produce green cementitious materials is an effective alternative to cement. This study utilizes steel slag (SS) and calcium carbide residue (CCR) as alkaline activators, combining them with blast furnace slag (BFS) and fly ash (FA) to create SCBF cementitious materials. Investigate the flowability, setting time, rheological properties, compressive strength, pore structure, and microscopic morphology of SCBF cementitious materials under different conditions and conduct molecular dynamics simulations. The research findings indicate that with an increase in BFS content, the flow performance of SCBF decreases, setting time shortens, plastic viscosity and yield stress gradually increase, UCS increases, and the proportion of harmful pores inside the samples decreases. When SS:CCR:BFS:FA is at a ratio of 25:25:30:20, with an increase in curing temperature, the UCS of samples shows a trend of first increasing and then decreasing. The proportion of harmful pores follows a pattern of initial decrease followed by an increase. When the curing temperature is 30 °C, the proportion of harmful pores is 0.31 %, reaching a local minimum, and the UCS strength reaches 13.83 MPa. In the raw materials, SiO2 and Al2O3 aggregate with Ca2+ in an alkaline environment to form C-(A)-S-H three-dimensional network gel. The potential energy, kinetic energy, non-bonding energy, and total energy of Tobermorite 14 Å crystals gradually increase with higher curing temperatures, with the most intense molecular motion occurring at 60 °C. The research findings are beneficial for promoting the use of industrial solid waste to manufacture green cementitious materials as substitutes for cement-based materials. They also provide a theoretical basis for the industrial application of high-temperature-cured solid waste cementitious materials.