We report on the discovery that paraffins and olefins up to C6 hydrocarbons can be obtained in CO2 electroreduction at room temperature and atmospheric pressure by application of a commercially available Cu-electrode (Eurofysica), provided pretreatment by electropolishing is avoided. The product distribution follows the Schultz–Flory distribution and, depending on the applied potential, the chain growth probability (?) ranges from 0.23 to 0.31, values lower than those obtained in Fischer–Tropsch synthesis over heterogeneous Co- or Fe-based catalysts.