This study describes a novel experimental apparatus for monitoring electrochemical reactions by in situ NMR spectroscopy. A unique cylindrical 3D-printed electrochemical cell, incorporating a reference electrode, was developed to enable electrochemical measurements through exact potential control. The performance of the novel cell is demonstrated by monitoring ethanol electrooxidation, an important process in fuel cell technology. Ethanol electrooxidation reaction utilizing the UiO-66/Pt/Vulcan XC 72R catalyst was monitored for more than 70 h, providing significant insights into catalyst efficiency, deterioration, and reactivation. This novel methodology fosters the potential of in situ electrochemical investigations, thus widening the applicability in electrocatalysis research.