Carbon capture and utilisation technologies are being investigated as potential pathways to support CO2 management and the production of chemical feedstocks using low-carbon electricity. Electrochemical CO₂ reduction (eCO2R) is a potential pathway that can use low-carbon electricity to convert CO₂ into value-added chemical feedstocks, in turn, be further upgraded via chemical or biological pathways. Cu-based catalysts have been extensively studied for eCO2R into C1 and multi-carbon products, due to the role copper plays in C-C coupling. Consequently, there is significant interest in exploring Cu-based electrocatalysts, aiming to improve product selectivity and better understand factors that influence the potential technoeconomic performance of these systems. 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 electro-catalysis process.