The metabolism of 7-(4-chlorbenzyl)-7,8,13,13a-tetrahydroberberine chloride (CTHB), a compound with promising pharmacological effects against arrhythmia, was investigated in rat bile. A metabolite and unchanged CTHB were found in the bile. Characterization and structural elucidation of the metabolite was achieved by LC/MS and LC/NMR. The following metabolic pathway is proposed: CTHB is metabolized by demethylation at position 10 to produce a new entity.