Twenty-seven alkaloids were identified from the stem-bark of Erythroxylum zambesiacum by GC and GC-MS. The characteristic alkaloids were tropane derivatives, together with nicotine. In addition to known substances previously isolated from the root-bark, a further 20 alkaloids were identified in the stem-bark. The principal base was 3α-(3′,4′,5′-trimethoxybenzoyloxy) tropane. Additionally, three new alkaloids were characterized as 6β-benzoyloxytropan-3-one and, tentatively, 6-isovaleryloxytropan-3-ol and 3-(2-methylbutyryloxy)tropan-6,7-diol. © 1993.