Six of the major vitamers and provitamins comprising vitamin A (β-carotene, retinoic acid, retinol, retinyl palmitate, retinyl acetate, and retinal) were examined using voltammetric and controlled potential electrolysis techniques in the aprotic organic solvents acetonitrile and dichloromethane at glassy carbon and platinum electrodes. All of the compounds underwent oxidation and reduction processes and displayed a number of similarities and differences in terms of the number of redox processes and chemical reversibility of the voltammetric responses. The electrochemical properties of the compounds were strongly influenced by the functional groups on the unsaturated phytyl chains (carboxylic acid, alcohol, ester, or aldehyde groups), and not only on the fully conjugated hydrocarbon unit which is common to all forms of vitamin A. The compounds were reduced at potentials between approximately -1.7 and -2.6 vs (Fc/Fc(+))/V (Fc = ferrocene) and oxidized at potentials between approximately +0.2 and +0.7 vs (Fc/Fc(+))/V. The average number of electrons transferred per molecule under long time scale electrolysis experiments were found to vary between 0.4 and 4 electrons depending on the exact molecular structure and experimental conditions.