One way of increasing access to electricity for impoverished unconnected areas without adding significant amounts of CO₂ to the atmosphere is by promoting renewable energy technologies. However, decision-makers rarely, if ever, take into account the level of in-built energy requirements and consequential CO₂ emissions found in renewable energy, particularly photovoltaic cells and related equipment, which have been widely disseminated in developing countries. The deployment of solar panels worldwide has mostly relied on silicon crystalline cell modules, despite the fact that less polluting material—in particular, thin film and organic cells—offers comparatively distinct technical, environmental and cost advantages characteristics. A major scientific challenge has thus been the design of a single decision-making approach to assess local and global climate change-related impacts as well as the socio-economic effects of low-carbon technology. The article focuses on the functions of the multi-criteria-based tool SURE-DSS and environmental impact analysis focused on greenhouse gases (GHG) emissions balance to inform the selection of technologies in terms of their impact on livelihoods and CO₂eq. emissions. An application in a remote rural community in Cuba is discussed. The results of this study show that while PV silicon (c-Si), thin film (CdTe) and organic solar cells may each equally meet the demands of the community and enhance people’s livelihoods, their effect on the global environment varies.