Studies employing electrochemical reduction at mercury electrodes, carbon-13 nuclear magnetic resonance spectroscopy, mass spectrometry, and other techniques have contributed to an understanding of the solution chemistry of the anabolic steroid oxymetholone (17-hydroxy-2-(hydroxymethylene)-17-methyl-5α,17/β-androstan-3-one). The compound can exist in three tautomeric forms, IIII. In mixtures of aqueous buffer and acetonitrile, the gemina! diol of form III is electrochemically reducible. In mixtures containing methanol or ethanol, a hemiacetal VI is formed, which is in slowly established equilibrium with the hydrate. Two separate peaks in differential pulse polarography show establishment of the equilibria between the hydrate and the hemiacetal, whereas UV spectra show overlapping peaks. An approximate value K = 0.29 has been found for the equilibrium constant K=[hemiacetal] [H2O]/[hydrate] [CH3OH]. Interaction of oxymetholone with alcohols was confirmed by mass spectra of reaction products. 13C NMR spectra indicate that addition of methanol also occurs in chloroform solutions. Electrochemical studies enhance the observation of an unexpected chemical reaction.