Three new stereoisomeric steroidal alkaloids, viz. solacapine (6), episolacapine (11), and isosolacapine (13), along with another hitherto unreported base, O-methylsolanocapsine (3), have been isolated from the arboreal part of Solanum pseudocapsicum Linn. They have been characterised as (20S, 22R, 23S, 25R)-, (20S, 22R, 23R, 25R)-, and (20S, 22S, 23S, 25R)-3β-amino-16α,23-dihydroxy-22,26-epimino-5α-cholestanes, respectively, primarily based on ¹H and ¹³C n.m.r. spectra. The structures of (3), (6), and (11) could be confirmed by correlation with solanocapsine (1). Isosolacapine (13) turned out to be the first 22,26-epiminocholestane derivative encountered in nature with 22βN stereochemistry. A diagnostic down-field shift of the C-22 resonance frequency in the ¹³C n.m.r. spectra of 22βN-22,26 epiminocholestanes by ca. 3 p.p.m. relative to those of the corresponding 22αN-isomers has been observed. The C-25 stereochemistry of solanogantamine (28) and isosolanogantamine (29), the stereoisomeric 3-amino solanidanes isolated from Solanum giganteum Jacq., has also been established.