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Abstract:The use of carbon dioxide, the most concerning environmental issue of the 21st century, as a feedstock for fuels productions still represents an innovative, yet challenging, task for the scientific community. CO 2 photoreduction processes have the potential to transform this hazardous pollutant into important products for the energy industry (e.g., methane and methanol) employing a photocatalyst and light as the only energy input. In order to design an effective process, the high sustainability of this reaction should be matched with the perfect reaction conditions to allow the reactant, photocatalyst, and light source to come together: therefore, the choice of reaction conditions, and in particular its medium, is a crucial issue that needs to be investigated. Throughout this paper, a careful study of carbon dioxide photoreduction in liquid and vapour phases are reported, focusing on their effect on catalyst performances in terms of light harvesting, productivity, and selectivity. Different from most papers in the literature, catalytic tests were performed under extremely low light irradiance, in order to minimise the primary energy input, highlighting that this experimental variable has a great effect on the reaction pathway and, thus, product distribution.