This study aims at assessing the possibility to produce value-added fuels from carbon dioxide (CO(2)) and non-fossil hydrogen (H(2)). Ethanol synthesis is an economically attractive route for CO(2) recycling. The proposed process includes three phases: [1] hydrogen generation by solar water splitting in the photo-electrocatalytic cells (PEC), [2] conversion of CO(2) to carbon monoxide (CO) by the reverse water-gas shift reaction (RWGS) using previously obtained H(2), and [3] ethanol synthesis from the synthesis gas (CO + H(2)). A first simulation model of the process was carried out with Aspen Plus (R) software in order to investigate the quantitative and qualitative evolutions of the reaction products. Furthermore, a parametric study was conducted in order to specify the influence of the temperature, pressure, and reagents' ratio.