The purpose of this research is to establish and optimize a new method for accurate and rapid capillary electrophoresis-chemiluminescence detection of fumonisin B₁.Methods The conditions for luminescence were optimized based on the effect of fumonisin B₁ on the chemiluminescence system of Ag(Ⅲ) and lumonol. The buffer solution was 2×10-3 mol/L luminol solution containing 5×10-3 mol/L borax, and the oxidation reagent was the 3×10-5 mol/L Ag(Ⅲ) solution containing sodium hydroxide. Results After optimization of separation and detection, the linear range was from 1 to 200 μg/ml, and the detection limit (S/N=3) was 1 μg/ml. On the eight parallel detections of 200 μg/ml fumonisin B₁, the relative standard deviations of peak time and peak height were 2.64% and 7.86%.Conclusion The method is simple, rapid, accurate and reliable for the detection of fumonisin B₁, and could be applied to detect fumonisin B₁ in corn.