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In this paper 1-(2-pyridylazo)-2-naphthol (PAN) and ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF4) were mixed with graphite powder to get a modified carbon paste electrode (PAN-1L-CPE), which was further used for the sensitive determination of bismuth(Ⅲ). By the co-contribution of the formation of PAN-Bi complex and the accumulation effect of IL, more bismuth(Ⅲ) was electrodeposited on the surface of the PAN-IL-CPE. Then the reduced Bi was oxidized and detected by differential pulse anodic stripping voltammetry (DPASV) with the oxidation peak appeared at 0.17 V (vs. SCE). Under the optimal conditions the oxidation peak current was proportional to the bismuth(Ⅲ) concentration in the range from 0.04 to 7.5 μM with the detection limit as 3.9 nM. The proposed method was successfully applied to the stomach medicine sample detection with good recovery.