To the best of our knowledge, this study proposes the first example of a covalently bound organometallic complex employed for CO2 reduction in the presence of amines in methanolic medium. Compared to previous integrated CO2 capture and electroreduction processes, the current system opens the possibility of scaling up the entire carbon capture and recycling process employing a cost-effective Mn-based electrocatalyst. The abrupt increase of FEHCOO-and TONHCOO─ values obtained by employing PMDETA as additive represents a breakthrough in CO2 catalytic activation. The experimental data is supported by DFT calculations, which indicate a barrierless conversion of CO2 to formate in our operating conditions. A lock-and-key mechanism effectively explains the role of CO2loaded amines in the activation of either dipolar (methanol) or quadrupolar (CO2) substrates towards the reaction with the Mn catalyst.