Berberine was extracted fromCoscinium fenestratum(tree turmeric) and purified by column chromatography. The UV-Vis absorption spectroscopy of berberine was studied in acetonitrile and aqueous media. TD-DFT calculations employing the B3LYP functional were found to reproduce the general features of the absorption and emission spectra correctly. The electronic transitions to the first and second excited singlet states involve a transfer of electron density from the electron donating methylenedioxy phenyl ring to the electron accepting isoquinolium moiety. An estimate of the electrochemical gap (2.64 V) was obtained from microelectrode voltammetry and good agreement was found with quantum chemical calculations using the cc-pVTZ basis set and the B3LYP, CAM-B3LYP and wB97XD functionals. The calculations indicate spin density of the radical dication is delocalised over the molecule. These basic data are useful for assessment of the synthesis of donor–acceptor polymeric materials employing oxidative polymerization or co-polymerisation of berberine.