Pulsed electrolysis, the application of alternating potentials has garnered interest in the CO2 reduction community as this technique can afford a rational route to modulate product selectivity, stability, and activity (Fig. ). However, the community's understanding of how pulse impacts underlying physicochemical processes in the dynamic microenvironment near the catalyst surface is being developed (Fig. ). To this end, operando techniques, those performed as the reaction is occurring, help elucidate the identity of catalyst phase and reaction intermediate coverage. In this work, we make use of synergy between pulsed electrochemistry and operando techniques (X-ray diffraction (XRD), Raman, infrared (IR) spectroscopy) to select conditions to modulate the reaction intermediate coverage during our electrosynthetic reaction to promote C-N coupling. We use Cu nanoparticles as a model catalyst, CO2 as the C-reactant and NH3 as the N-reactant to carry out C-N coupling. We select optimized conditions in which we maintain a steady-state coverage of *NH2 while maintaining Cu in the metallic state and show how pulsed electrolysis increased both the formation rate and selectivity for C-N products of urea, formamide and acetamide by factors of 3-20 (Fig. ). The synthetic value brought by this new approach is further demonstrated through the expansion of scope to additional C-and N-reactants and even to C-S coupling. We next investigated the effects that electrochemical pulsing would have on the performance of the system towards electrosynthetic C-N bond formation. We used static potential electrolysis with Eca=1.8 V as the reference point and used systematically varied Ean potentials with t=1s for both Eca and Ean. Liquid C-N products were measured through NMR and their presence was confirmed through a combination of isotope labelling, 2D NMR (Fig. -18). While the Faradaic efficiency (FE) for C-N products was generally below 3% for the sum of C-N products under static conditions, the application of pulsing significantly increased this by factors of approx. 3-20 up to a maximum of 33% (Fig. ). Notably, urea and methylamine were relatively minor products under steady state electrolysis, but their selectivity significantly increased when pulsing was applied. We found that urea selectivity was maximized in 1 M KOH and 1.5 M NH3, while acetamide selectivity increased with 0.1 M KOH was used and decreasing the NH3 concentration to 1 M maximized formamide selectivity. Methylamine was present in all conditions as a minor product. Similarly, we plotted the formation rates for all C-N products and similar enhancement rates were evident. The variation of C-N product selectivity as a function of electrolyte composition and Ean points to the sensitivity of the electrosynthetic system's performance to *NH2 and CO2R intermediate coverage, Cu oxidation, and local pH and double layer composition at the Cu surface. The Faradaic efficiency (FE, b) and product formation rate (FR, c) for C-N products under three model conditions is significantly enhanced relative to that when using static potentials. For clarity, the FRs of methylamine are multiplied by factor 10. Potentials are referenced to Ag/AgCl. Next, the system was probed under typical catalytic conditions (1M KOH, 1.5M NH3) to visualize the interplay of catalyst phase and surface reaction intermediates potentially responsible for C-N bond formation. XRD spectra, taken at 5-minute time intervals after setting a pulsing potential, show that surface oxides are reduced away within 10 minutes at -1.8V (Fig. ). The only detectable phase is metallic Cu until Ean=0.4 V at which Cu2O begins to grow. This indicates that Cu is the predominant active site for this reaction. However, as a pulsed potential was applied, a tensile strain of up to 1.0% was evident as the Cu(111) peak increasingly shifted from 44.3 to 43.9 o as Ean was set more positive, which may have a secondary effect on the Cu catalytic properties. Raman spectroscopy was next utilized to visualize reaction intermediates and near-surface species. Similarly, Cu2O was reduced away when negative potentials were applied, and bands attributed to Cu-X species were noted (320 cm -1 ) (Fig. ). Cu2O only reappeared at Ean=0.4, along with bands at 635 and 675 cm -1 attributed to Cu-OH and Cu-Oad. As Ean is progressively made more positive, the CO3 2-signals (band at 1067 cm -1 ) progressively diminishes and the HCO3 - signals (bands at 1018 and 1341 cm -1 ) grow , reflective of a pH increase at the surface. Bands at 983 and 1129 cm -1 may indicate *CHxO species as they have been previously assigned at these frequencies. At the higher frequency region, *CO2 -was noted (1540, 1584 and 1383) while new bands arising at 1454 cm -1 could stem from COOH vibrational modes as they typically fall within this spectral range (Fig. ). The peak at 1547 cm -1 may originate from C-N bond vibrational modes, as this peak shifts to 1512 cm -1 when 15 NH4Cl is used to replace the .