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Building stock modeling offers a useful tool for the assessment of scenarios to support decision makers in setting up effective strategies for meeting European and national targets for energy efficiency and decarbonization. One of the challenges faced for the reliable application of this modeling approach is the limited availability of detailed data for the investigated stocks. Earth observation can provide the means to respond to this challenge. This paper describes a procedure that exploits open data and non-commercial tools provided by geographic information systems to extract relevant information about the architectural characteristics of the buildings in a city block and assess the potential for CO2 emissions reduction from the installation of photovoltaics on building rooftops.