The reduction and oxidation potentials of methylated 4-styrylpyrylium and 6-styrylpyrylium perchlorates have been evaluated using cyclic voltammetry, in comparison to their non-methylated derivatives values. The reduction peak of all studied compounds remained chemically irreversible. The presence of the electron-donating methyl group on pyrylium ring leads to a shift of the styrylpyrylium perchlorates reduction potential towards cathodic values. Kinetic studies on platinum electrodes based on the variation of the peak potential at different scan rates and upon substrate concentrations confirm, in another way, the mechanism of electron transfer. KEY WORDS: Styrylpyrylium perchlorates, Cyclic voltammetry, Reduction potential, Kinetic study Bull. Chem. Soc. Ethiop. 2013, 27(1), 117-124.DOI: http://dx.doi.org/10.4314/bcse.v27i1.12