The increased scrutiny over carbon emissions and management prompted the scientific community to search for efficient carbon dioxide (CO2) valorization technologies. Among them, the electrocatalytic CO2 reduction (eCO2R) into C2+-products powered by renewable electricity has recently been promoted, especially over Copper (Cu)-derived catalytic materials. However, finding an appropriate balance between the overall activity and desirable C2+-products’ selectivity remained challenging. To overcome this, the catalysis community often provides elegant, yet neither scalable or affordable, solutions. Moreover, these sophisticated catalytic materials were often sourced from fossil resources or undergo energy-intensive synthetic manipulations, emitting more CO2 than it could possibly consume via subsequent eCO2R. Therefore, we demonstrate in this work that atacamite (Cu2(OH)3Cl) supported over inexpensive precipitated calcium carbonate delivers superior performance towards C2+ products preferentially (cf. 32% of faradaic efficiency) at −1 V versus reversible hydrogen electrode with durable lifetime. Additionally, numerous characterization tools were employed to identify its structure-performance correlation.