Ionization potentials I-p, electron affinities E.A., and the quantum confinement in CdSe nanocrystals were determined by means of cyclic voltammetry. The results were compared to values obtained from spectroscopic measurements, especially UV/vis absorption and photoluminescence emission spectra. Absolute band gap positions were obtained from the electrochemical measurements and discussed with regard to vacuum level values. The results are in good agreement with theoretical expectations and spectroscopic data. (C) 2003 American Institute of Physics.