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Despite geopolitics play a pivotal role in the energy sector, geopolitical aspects are often not considered in the quantitative assessment models aimed at supporting the energy investment decision-making process. To address this issue, this work proposes an Extended Multi-regional Input-Output model (EMRIO) that incorporates import dependence and governance along the value chain. As case study, two alternative energy investments in Mexico – a Natural Gas Power plant (NG) and a Concentrated Solar Power plant (CSP) – are assessed. The method quantifies the geographical diversification of suppliers and the quality of governance. The assessment of the case study shows that the supply chain of the CSP plant includes more countries and with better governance levels than the supply chain of the NG power plant. That means, a priori, that the supply risks of investing in CSP power plants will be lower, as will suppliers' endogenous geopolitical risk. However, a sensitivity analysis considering different providers of the solar plant components reveals that CSP plant value chain could also entail similar or even higher governance risks levels as the NG plant. The scenario where China provides some of the components entails a much higher governance risks, even higher than the NG base case. In consequence, we have proved that the method proposed allows the identification of hidden geopolitical risks that would otherwise go unnoticed. This paper enlarges the existing knowledge on assessment methodologies for energy policy decision-support by measuring diversification and imports dependence from countries with different levels of governance along the whole value chain. • Extended Multi-regional Input-Output model (EMRIO) is combined with two dependence metrics and six governance indicators. • Value chain risk analysis improves the sustainability assessment for decision-makers. • The CSP supply chain is more diversified and has better governance levels than NG. • Value chain governance indicators significantly worsen when China becomes component supplier. [ABSTRACT FROM AUTHOR]