This study evaluates the integrated sustainability potential of WtE technology scenarios across eight South African metropolitan municipalities, which collectively represent 40.14% of the national population. The assessment considers energy generation, greenhouse gas (GHG) emission reduction, landfill space savings, waste diversion, financial feasibility, and technology readiness, in alignment with the Waste-to-Energy Roadmap, National Waste Management Strategy, and Integrated Resource Plan. Seven scenarios were evaluated for the period 2028–2050, incorporating recovery rates that increase at 7–8-year intervals to ensure sustainable feedstock supply. These include S1 (Business-as-Usual/Landfilling), S2 (Landfilling with upgraded landfill gas recovery, LFG+), S3 (LFG+ with anaerobic digestion (AD)), S4 (LFG+ with AD and incineration), S5 (LFG+ with AD and pyrolysis), S6 (LFG+ with AD and gasification), and S7 (LFG+ with AD and plasma gasification). An Integrated Sustainability Performance Index (ISPI), combining 12 normalized energy, environmental, financial, and technological indicators, identified S4 as the most sustainable scenario, with an average score of 0.688 ± 0.044 and first-place ranking in all municipalities. S3 ranked second at 0.520 ± 0.085, while S7 ranked last. S2–S3 remained financially attractive, whereas advanced thermal technologies benefited municipalities with larger waste volumes. Integrated WtE systems support South Africa’s energy transition and sustainable waste management.