In this paper, we developed a direct way for the study of hydroquinone oxidation through in situ electrochemistry-combined nuclear magnetic resonance (EC-NMR). Electro-polymerization-induced nano-polyaniline film was utilized as the catalyst in the process of electrochemical oxidation of hydroquinone. In situ EC-NMR provides a powerful tool to probe products distribution and reaction rate, which could be useful to investigate electro-catalytic mechanism and evaluate the electro-catalytic capacity. To study the influence of both protic and aprotic media in the electrocatalytic process, we mixed water and dimethylsulfoxide to mimic possible real-life electrochemical environments. The proposed in situ EC-NMR is capable of quantitatively monitoring the generation of products under varied solvent composition and pH values. A positive effect to electro-catalysis capacity is observed when the concentration of DMSO or water is increased from the volume equivalent point, implying that there should be a competition between protic and aprotic media, which can be characterized by EC-NMR technique. (C) 2018 Elsevier Ltd. All rights reserved.