Electrocatalytic C–N coupling under ambient conditions from carbon dioxide (CO₂) and nitrogen species offers a sustainable route to commodity amines, amides, and carbamides; however, significant analytical hurdles remain due to the complexity of the product matrix. Accordingly, careful detection and characterization methods are essential to avoid inaccurate results. In this work, we present an optimized product detection method for acetamide, generated via the electrocatalytic C–N coupling reaction from CO₂ and nitrite (NO₂⁻), using nuclear magnetic resonance and Fourier–transform infrared spectroscopy. This acetamide structure was further validated through a single–crystal X–ray diffraction. Using a bimetallic PdBi catalyst, we achieved a Faradaic efficiency (FE) of 47% for acetamide at –0.6 V vs reversible hydrogen electrode (RHE). Our findings establish a high–performance catalytic system while providing a rigorous and widely applicable framework for analysing and quantifying elusive products in electrocatalytic C–N coupling.