Among other metal catalysts, Copper (Cu) is a well-known for electrochemical reduction of CO2 and its selectivity primarily governed by the applied electrode potential and yields a wide-range of gaseous and liquid products. Specifically, CO2 electroreduction to formic acid, carbon monoxide (CO) and methane were observed at low-potentials <-1.0 V RHE (1), whereas ethylene, ethanol and n-propanol were yielded at high-potentials >-1.0 V RHE (2). On the other hand, catalytic activity of Cu inherently contributes from mixed oxidation states, surface roughness and aspect ratio of nanostructures. Consequently, different strategies such as oxide-derived, mixed metal-oxides, electrooxidized or anodized Cu-surfaces have been investigated to tune its catalytic activity. In addition, Cu-surfaces of different morphologies - spikes, steps and edges, or its nanostructures having different shapes and dimensionality were thoroughly investigated. However, electrochemical performance of Cu-electrocatalysts eventually declines as surface morphology fades out and/or while Cun+ quickly retains its pure metallic-state during long-term electrolysis under electrochemical reduction potentials (3). Moreover, due to limited CO2 solubility in aqueous electrolytes and inability of Cu for direct-activation of gaseous-reactant (CO2(g)), these catalysts displayed low-throughputs (<30 mA/cm2). In this context, our research demonstrates how Cu-based perovskite-oxides of A2BO4-type, with Cu on B-site, are crucial for electrochemical CO2 reduction and its product selectivity. This presentation sheds light on how these catalysts are unique for fine-tuning Cu-oxidation state with control of lanthanum-elements (on A-site) and/or its partial doping with element of slightly different oxidation-number. This work specifically provides synthetic means of optimizing Cu-structure by relative-doping (x) in La2-xSrxCuO4±δ along with identification/preservation of responsible active-site and depicts the underlaying mechanistic aspects of CO2-electroreduction towards ethanol, n-propanol, and ethylene. The presentation also highlights how the overall oxygen deficient-sites (δ) created within the structure of A2BO4±δ are not only critical for direct activation of gaseous CO2, but also promote throughputs (up to 100-200 mA/cm2) required for commercial implementation.