The global surge in CO2 emission has been instrumental in perpetrating climate change and other environmental jeopardies. With about 40% of CO2 emission being contributed by the generation of electricity, it becomes imperative to emphasize on curbing electricity-related emission. The study undertakes decomposition analysis of CO2 emission of the highest three emitting countries, viz., China, the USA and India over the period 1992–2018 using variance analysis method. The major findings indicate that rising population and income are the driving forces of higher emission from electricity generation. However, China and the USA have made technological improvements to neutralize their emission to some extent, but India has hardly been able to perform remarkably in this regard. Unlike the other two countries, both the use of coal in electricity generation and emission intensity of coal in India has increased over time. The study attempts to identify the factors that can play a dominant role in harnessing rising emission in India and suggests policy prescriptions thereof.