Fluorescece spectroelectrochemistry is used to probe redox process of benzoquinone. The benzoquinone reduction state has a lower fluorescence quantum efficiency. CVF and DCVF can reveal more information about benzoquinone redox reactions. This method can analyze compounds with fluorescence and electrochemical activities. Quinones are common organic compounds frequently used as model dissolved organic matters in water, and their redox properties are usually characterized by either electrochemical or spectroscopic methods separately. In this work, electrochemical methodology was combined with two fluorescence spectroelectrochemical techniques, cyclic volta- fluorescence spectrometry (CVF) and derivative cyclic volta- fluorescence spectrometry (DCVF), to determine the electrochemical properties of -benzoquinone in dimethyl sulfoxide, an aprotic solution. The CVF results show that the electrochemical reduction of -benzoquinone resulted in the formation of radical anion and dianion, which exhibited a lower fluorescence intensity and red-shift of the emission spectra compared to that of -benzoquinone. The fluorescence intensity was found to vary along with the electrochemical oxidation and reduction of -benzoquinone. The CVF and DCVF results were in good consistence. Thus, the combined method offers a powerful tool to investigate the electrochemical process of -benzoquinone and other natural organic compounds.