The electroreduction of phenazine in basic mixtures of and 1‐ethyl‐3‐methyl‐1H‐imidazolium chloride (EMIC) (44.4 mole percent ) has been investigated by electrochemical and spectroscopic techniques. Initial results suggested that the reduction of phenazine proceeded through a two‐electron process coupled with two protonations to form dihydrophenazine. However, further investigation, using authentic dihydrophenazine, indicated that this reduction product was not the result of proton exchange reactions but rather a chloroaluminate species may be acting as the acidic entity in this liquid. The use of neat 1‐ethyl‐3‐methyl‐1H‐imidazolium hydrogen dichloride and mixtures of and 1,2‐dimethyl‐3‐propyl‐1H‐imidazolium chloride (DMPIC) as solvents for electrochemical investigations of dissolved organic substrates is also reported.