The root bark of Solanum aculeastrum Dunal yielded a new steroidal alkaloid glycoside characterised as (25R)-3β-{O-α-L-rhamnopyranosyl-(1→2)-[O-β-D-glucopyranosyl-(1→4)- O-α-L-rhamnopyranosyl-(1→4)]-β-D-glucopyranosyl}-22α-N-spirosol-5-ene. The structure was established by spectroscopic analysis and comparison with published data of similar compounds reported in literature.