Sterigmatocystin, ST, is carcinogenic mycotoxin with toxicity second to aflatoxins, contaminated in foods- and feeds-stuff widely. A three-electrode system was employed to examine the response character of the covalently united ADTZ–MWNTs electrode to ST, and the results indicated that an oxidation peak of ST was observed at about +400 mv, the linear detection range of ST was from 4.16×10 −5 mg/ml (0.13 μM) to 1.33×10 −3 mg/ml (4.29 μM) with the detection limit at 0.13 μM. Compared to the corresponding results obtained from the MWNTs modified electrode that ADTZ was directly sediment (adsorbed) on it, the sensitivity of ours had been improved by two orders of magnitude, which could provide some important data to further research.