Studying the evolution of the efficiency of the electricity generation sector is a relevant task for policy makers, and requires the undesirable outputs derived from the activity to be considered in the evaluation. In this work, we propose a dynamic slack-based Data Envelopment Analysis (DEA) model that incorporates the assumption of weak disposability between the generation of electricity from fossil sources and the CO2 emissions caused by the sector to measure the technical efficiency of 24 Latin American and Caribbean countries in the period 2000–2016. The results show that, of the total number of countries studied, four are efficient overall, and four groupings of countries in relation to the levels of efficiency achieved are also identified. These results are important given that less-efficient countries can, through learning, increase their efficiency in electricity generation or emulate the future strategies proposed by the most efficient countries.