To solve the problem of environmental pollution from stockpiling of solid waste and to achieve safe and efficient underground engineering, an environment-friendly waste-based ternary geopolymer grout was developed using BFS, SSA, and BRHA. KOH-activated grouts were used as the controls. The applicability of grouts with different SSA additions was also investigated. The results showed that the 28-day compressive strength of SSA-activated grout reached 24.31 MPa, which exceeded that of the control group by 163.7%. Potassium and calcium salts, such as fairchildite and magnesium potassium silicate, in SSA promoted the formation of C(K)-A-S-H and C-S-H gels. The carbon emissions calculated from global warming potential in the life cycle assessment of the SSA system were 83.5% lower than those of KOH. The leaching results showed that the concentration of all heavy metals dropped below 0.02 mg/L after 28 days of solidification. The immobilization efficiencies of Cr, Pb, and Zn exceeded 98.65%, indicating the considerable immobilization ability of the SSA-activated grout and that it can be used safely in further applications. These findings support the treatment of solid waste resources and preparation of high-performance grouts for underground engineering.