Waste-to-energy (WtE) technologies can offer sustainable solutions for waste that cannot be further reused or recycled, such as the part of municipal solid waste (MSW) that is not suitable for recycling processes. The two main (most widely used) thermal treatment technologies that can be applied to MSW are direct combustion in an incineration plant and gasification. This paper examines in particular the direct combustion in incineration plants, explaining the main process, the main technologies applied, and the resulting environmental aspects. Moreover, this work focuses on analyzing flue gas emissions from thermal treatment in order to better understand the impacts of these kinds of processes. A particular focus on the CO2 parameter is performed. CO2 is a persistent atmospheric gas, and it is one of the greenhouse gases (GHGs) potentially responsible for the climate change phenomenon. In this sense, specific indexes (tCO2/tMSW and tCO2/MWh) are elaborated considering the thermal treatment plants present in six Italian regions. The main aim of this review paper is to try to fill the gap that still exists regarding the emissions environmental compatibility coming from these type of plants, the evaluation of the amount of CO2 emitted, and the possible reduction of the CO2 parameter. One of the main outcome obtained is in fact the evaluation of the amount of CO2 coming from these kinds of plants and some indications about the technological possibilities of reducing this amount.