This study investigates the formation of a microenvironment at the nanoparticle-ligand interface through electrochemical bias-induced ligand detachment. Using in situ infrared nanospectroscopy (nano-FTIR) and surface-enhanced Raman spectroscopy (SERS), the researchers observed the consecutive bond cleavage of surface ligands, leading to the formation of an ordered ligand interlayer (NOLI). The NOLI is a highly active and selective microenvironment for CO₂ to CO conversion. The study reveals that the bias-induced dissociation of tetradecylphosphonic acid ligands results in the development of an electrocatalytic interlayer, which is stable near the Ag surface. The spatially resolved observations provide insights into the molecular-scale events that occur during the formation of the NOLI, offering fundamental knowledge for designing electrocatalysts with tailored functionalities. The methodology used in this study can be applied to investigate the dynamic response of various interfacial species to external stimuli, advancing the understanding of molecular-level events leading to specific NP functionalities.This study investigates the formation of a microenvironment at the nanoparticle-ligand interface through electrochemical bias-induced ligand detachment. Using in situ infrared nanospectroscopy (nano-FTIR) and surface-enhanced Raman spectroscopy (SERS), the researchers observed the consecutive bond cleavage of surface ligands, leading to the formation of an ordered ligand interlayer (NOLI). The NOLI is a highly active and selective microenvironment for CO₂ to CO conversion. The study reveals that the bias-induced dissociation of tetradecylphosphonic acid ligands results in the development of an electrocatalytic interlayer, which is stable near the Ag surface. The spatially resolved observations provide insights into the molecular-scale events that occur during the formation of the NOLI, offering fundamental knowledge for designing electrocatalysts with tailored functionalities. The methodology used in this study can be applied to investigate the dynamic response of various interfacial species to external stimuli, advancing the understanding of molecular-level events leading to specific NP functionalities.