The electrochemical behavior of menadione reduction (MQ) in the presence of alkylated derivatives of the following nucleobases is reported for the first time in the present work: 9-nonyladenine (NAH), 1-nonylthymine (mTu), 1-ncr.ylcytcr!nc (NMI), aid 9-plienyietiviguamne (PEGH). Through voltammetric simulation, it was possible to characterize the MQ reduction mechanisms in the presence of NAH and NCH, including the hydrogen -bonding association between reduced species of menadione and nucleobases. In the case of the NAH nucleobase, the best fit between the simulated and the experimental voltammograms was achieved when a comproportionation reaction involving MQ(2-) (NAH) and MQ(-) is considered. The analysis of MQ voltammograms with different NTH concentrations led to the formation of an MQ(-)(NTH) association complex, and the concerted reduction and deprotonation of MQ(-) (NTH) resulted in the protonated species MQH(-), in agreement with the literature. Finally, in the case of the reduction of MQ with PEGH, the voltammetric response, evinced the protonation process of the semiquinone and confirmed a second -order disproportionation mechanism.