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Energy and water security are arguably among the most important present-day societal and environmental challenges. Amidst the early signs of human induced climate change, both energy and water management systems are undergoing sizeable transformations. In addition, water is a critically important resource for hydro- and thermoelectricity generation; fossil fuel extraction/processing, and for the production of biofuels. This paper analyses inter-dependences of energy and water in the Po River Basin District (PRBD) situated in the Northern Italy, the most industrialised part of the country and home to 17 million people. Specifically, we explore the role of climate variability as a part of the structural vulnerability of thermo- and hydroelectricity generation.