Solanidine, leptinidine, and acetylleptinidine from Solanum chacoense Bitter were structurally characterized by high-resolution MS and high-field 1H-NMR and 13C-NMR. 1H-NMR and 13C-NMR chemical shifts were assigned for solanidine and acetylleptinidine using DEPT, HMBC, and HMQC. Complete carbon chemical shift assignments are presented for all three alkaloids. The orientation of the C-23 acetoxyl group of acetylleptinidine was determined to be axial.