The most challenging deal we face these years is the need to lower greenhouse gas (GHG) emissions and tackle climate change; though calls to reduce it are growing louder yearly, emissions remain high. CO₂ is the key contributor. For this reason, synthesising high-added-value products from CO₂ conversion is a promising approach to mitigate the problem. [1] Among the different alternatives, exploiting CO₂ via electrochemical reduction under mild conditions (ambient pressure and temperature) represents an opportunity to support a low-carbon economy.[2] The electrocatalytic (EC) CO₂ reduction (CO₂R) driven by renewable energy can be exploited for the future energy transition, for the carbon storage into valuable products like syngas (H₂/CO mixtures), organic acids (formic acid) and chemicals/fuels (C₁₊ alcohols). A big challenge for the industrialisation of this technology is to find low-cost electrocatalysts, efficient reactors and process conditions. In the efforts to develop efficient, selective and stable materials, we have exploited the current knowledge of thermocatalytic CO₂ hydrogenation to develop noble-metal-free CO₂R electrocatalysts. For instance, Cu/Zn/Al synthesised catalyst producing methanol and CO from the CO₂ thermocatalytic (TC) hydrogenation (at H₂ pressure (P) of 30 bar and temperature (T) > 200 ^oC) promotes the formation of methanol (⁓32% of FE) during the EC CO₂R in a gas-diffusion-electrode system; while operating in the liquid phase, the same catalyst produces syngas with a tunable composition (95% of FE at the most positive applied potential) and other liquid C₂₊ products (in both cases at ambient T, P).[3]  Conversely, Cu/ZnO electrocatalyst has also been tested at industrially relevant current densities in liquid phase configuration.[4]  We demonstrated through ex-situ characterisations that the presence of ZnO nanoparticles in the mixed Cu/ZnO catalyst plays an important role in forming and stabilising mixed oxidation states of copper and Cu¹⁺/Cu⁰ interfaces in the electrocatalyst (in bulk and surface). These interfaces seem to promote CO dimerisation to ethanol. Indeed, ethanol was produced with the Cu/ZnO catalyst, reaching ethanol productivity of about 5.3 mmol∙g_cat^-1∙h^-1 in a liquid-phase configuration at ambient conditions. The Cu/Zn/Al and Cu/ZnO electrocatalysts have also been tested in a catholyte-free configuration with an increased selectivity to ethylene, reaching approx. 60% and 70% of FE, respectively. Here, Cu catalyst structure transformed, on average, completely to metallic with a very thin layer of Cu¹⁺ during testing, which seems to promote the selectivity towards C₂H₄, demonstrating that the reaction pathways for EC CO₂R are determined mainly by transport limitations rather than only by the intrinsic properties of the electrocatalysts. Our results open a promising path for the prospective implementation of metal-oxide nanostructures for CO₂ conversion to the chemicals and fuels of the future.