Brazil presents a high share of renewable electricity generation, mainly due to its favorable hydroelectric potential. However, reports estimate that demand will grow substantially in the long term, requiring a significant diversification of the electricity mix. In this context, this paper analyzes how the environmental impacts of electricity generation tend to change over the horizon 2025–2050 in Brazil and identifies improvement opportunities accounting for environmental and economic factors. To do so, the Open Source Energy Modeling System (OSeMOSYS) is applied to estimate the composition of the electricity mix in 2050. Then, life cycle assessment (LCA) is used to evaluate the associated environmental impacts across ten categories. Lastly, hybrid weighted ɛ-constraint multi-objective optimization (MOO) is employed to evaluate which sources can be used to minimize climate change and the levelized cost of electricity while ensuring that other categories are reasonably restrained. The results indicate that the environmental performance of the Brazilian electricity matrix tends to deteriorate substantially, both when analyzing overall impacts and impacts per kWh. Moreover, the proposed MOO approach suggests that some sources, mainly hydropower, onshore wind, and centralized PV present an all-around economic/environmental performance and might be favorable for expanding the power system.