The preparative electrochemical reduction of a series of anthracycline antibiotics was performed using the technique of large scale electrolysis and d. c. polarography for recording different reaction pathways. The reduction products were identified by mass spectrometric and chromatographic analyses. Only anthracyclines with sugar residues in the C-10 position (iremycin, roseorubicin A) were reduced reversibly by 2e- to the corresponding hydroquinones. All others with sugar residues in the C-7 position (daunomycin, 5-iminodaunomycin, adriamycin, carminomycin, β-rhodomycin II, aclacinomycin A, 1-deoxypyrromycin) showed an irreversible behavior because of the reductive splitting of the glycosidic bond under formation of 7-deoxy compounds or-if the C-11 OH-group was not present-of dimers, respectively.