The title steroidal compound, C31H49NO5, resulted from the selective oximation of (23R)-23-acetylsarsasapogenin acetate. One- and two-dimensional 1H and 13C NMR spectra, as well as IR data, are in agreement with the presence of a ketoxime group at C-23. However, recrystallization in slightly acidic media affords the title compound in the rare zwitterionic oxime form, as a consequence of migration of the hydroxy H atom to the N atom in the oxime group. This H atom is clearly detected and its position was refined from X-ray data. The geometry for the C=N+(H)—O group features long C=N and short N—O bond lengths compared to non-zwitterionic oximes. The ketoxime is stabilized with the E configuration, avoiding steric hindrance between the oxime O atom and H atom at C-23. The sum of the angles around the oxime N atom is 359.6°, giving a planar configuration for that atom, as expected for sp2 hybridization.