Nonaqueous capillary electrophoresis coupled to UV detection is described for the separation and determination of steroidal alkaloids. After optimization of electrophoretic parameters, including the electrolyte nature and the organic solvent composition, a reliable separation of solasodine and solanidine was achieved in a methanol-acetonitrile (20:80, v/v) mixture containing 25 mM ammonium acetate and 1 M acetic acid. For quantitative purpose, a fused-silica capillary with a bubble cell was used and detection was performed at low wavelength (195 nm). Method performances, including migration time and peak area reproducibility, linearity, sensitivity and accuracy, were also evaluated. The method was applied to determine solasodine in Solanum elaeagnifolium berries and Solanum sodomaeum leaves and seeds. To further improve sensitivity in the analysis of solasodine-related compounds, solanidine, demissidine and tomatidine, the developed method was interfaced with electrospray ionization mass spectrometry. In the case of solasodine, the detection limit was estimated at 3 μg/ml for NACE-UV and at 0.05 μg/ml for NACE-MS, in the selected ion-monituring mode.