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This paper aims to analyze the photovoltaic electricity energy expansion and recent data about the behavior of the CO2 emissions in Brazil and other selected countries. Data were collected from different bases as International Energy Agency (Agência Internacional de Energia), Ministry of Energy and Mines (Ministério de Minas e Energia), Research Electric Company as well as other papers in the field. Kaya Identity was applied as basis in order to evaluate the CO2 emissions. As a result, it could be seen a clear domain of Germany and Italy in the photovoltaic generation sector, with high investments in the development and dissemination of that technology. Brazil presented an energetic matrix of low carbon but with a tendency to increase emissions per capita throughout the years. The effect of decoupling between the greenhouse gas emissions and the large-scale economic development was checked. It was realized that that phenomenon tends to intensify it since renewable energy technologies get higher levels of use.