The influence of lithium ion pairing on the voltammetric reduction of anthraquinone in acetonitrile is reported. On gold electrodes, the single electron reduction generates a radical anion which forms a complex with lithium cations from the electrolyte. In situ ESR studies support this finding, and signal intensity measurements are used to estimate a value for the complexation equilibrium constant. Values calculated were of the of the order of 6000 mol(-1) dm(3). Potential shift measurements and Digisim modeling are shown to be in support of a complexation mechanism in which a little of the complex precipitates on the electrode surface. The effect of lithium ion pairing is also demonstrated for the case in which 1-anthraquinonyl groups are covalently attached to multiwalled carbon nantubes abrasively immobilized on a basal plane pyrolytic graphite electrode.