Globally, rising population and rapid urbanisation have resulted in the dual issues of increased electricity demand and waste generation. These exacerbate diverse global problems, ranging from irregular electricity supply and inadequate waste management systems to water/air/soil pollution, climate change, etc. Waste-to-Energy (WtE) approaches have been proposed and developed to address simultaneously these two issues through energy recovery from waste. However, the variety of available waste materials and different WtE technologies make the choice of an appropriate technology challenging for decision-makers. The evaluation of the different WtE technologies in terms of their sustainability could provide a solid comparative base for strategic decision making in the power and waste management domains. This paper presents research conducted using a multidimensional Life Cycle Sustainability Assessment (LCSA) approach to estimate and compare the environmental, economic, and social impacts associated with the generation of electricity from Municipal Solid Waste (MSW) in two major cities, Lagos and Abuja, in Nigeria. These cities provide case studies in a developing world context to explore how their similarities and differences may influence the LCSA impacts for four WtE systems (Anaerobic Digestion, Incineration, Gasification, and Landfill Gas to Energy), and this is the first research of its kind. An LCSA ranking and scoring system and a muti-attribute value theory (MAVT) multi-criteria decision analysis (MCDA) were employed to evaluate the overall sustainability of the prospective use of WtE over a 20-year timeframe. The results from both approaches indicated that the adoption of WtE offered sustainability benefits for both cities, marginally more so for Lagos than Abuja. It was concluded that, for optimal benefits to be achieved, it is vital for decision-makers to think about the various trade-offs revealed by this type of analysis and the varying priorities of relevant stakeholders.