Sustainable CO2 management based on carbon capture and utilisation technologies has gained considerable interest due to its critical role in resolving emission control and energy supply challenges. Electrochemical CO₂ reduction (eCO2R) is a promising pathway, where renewable energy is used to drive electrochemical CO₂ conversion into value-added chemical feedstocks that can, in turn, be further upgraded via chemical or biological pathways. Cu-based catalysts have been extensively studied for eCO2R into C1 and multicarbon products, due to the role copper plays in catalysing C-C coupling. Consequently, there is significant interest in exploring Cu-based electrocatalysts to enhance product selectivity, aiming to maximise both economic and environmental advantages. The challenge lies in addressing the high overpotential and poor selectivity in eCO2R. On the other hand, understanding the structure-activity relationship of Cu-based catalysts utilised in eCO2R is also an essential aspect for tuning catalyst selectivity to maximise the desired product yield. This work investigates the changes in product distribution on different Cu-based electrocatalysts such as Cu-based nanoparticles and Cu complexes. Additionally, we analysed the structural characterisation of Cu2O as a representative catalyst through advanced techniques such as Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) equipped with Electron Energy Loss Spectroscopy (EELS), and X-ray Diffraction (XRD). These methods enabled visualising the catalyst structure and understanding how structure changes affect their catalytic activities. Furthermore, our findings demonstrate how microscopic imaging can inform catalyst restructuring by capturing the changes occurring during the catalysis process.