The net increase in atmospheric greenhouse gas concentrations adversely affects air quality, human health, and energy security. Electrochemical CO2 reduction is a promising way of converting this greenhouse gas to value-added chemicals and fuels. The present study considers electrochemical CO2 reduction with silver electrodes in aqueous electrolytes. Silver exhibits good selectivity towards carbon monoxide, so its separation is more straightforward. CO is an important carbon intermediate used to produce chemicals such as acetic acid, phosgene and furthermore, mixtures of H2 and CO (syngas) can be used to produce higher hydrocarbons and combustion fuels via Fischer-Tropsch process. Literature suggests CO is produced on the electrode surfaces via a few adsorbed species, and the mechanistic studies are mainly based on density functional theory (DFT) calculations of reaction path-free energies as a function of the reduction potential. This study uses experimental techniques coupled with modeling studies to elucidate the detailed mechanism of electrochemical CO2 reduction to CO using planar silver electrodes. The slow mass transport of sparingly soluble gases to conventional planar electrodes hinders the practical implementation of this technique. A gas diffusion electrode (GDE) will be a suitable option to overcome this mass transfer limitation, and the electrolyzer can also be operated at higher current densities. The selectivity and activity of metal catalysts like tin and copper are enhanced in their respective oxide forms. This study also proposes to evaluate the role of AgOx in CO2R in a GDE-based electrolyzer.