On the basis of a chemically modified platinum electrode by europium （Ⅲ）-doped Prussian blue analogue film（Eu-PB） as a working electrode，a rapid and sensitive method for the determination of polyoxin B was established using capillary electrophoresis coupled with electrochemiluminescence detection（CE-ECL）.Parameters related to the separation and detection were discussed and optimized.The possible mechanism of ECL was briefly discussed.Under the optimized conditions（ECL detection potential at 1.27 V，electrokinetic injection for 10 s at 8.5 kV，16 kV as the separation voltage，20 mmol/L pH 8.5 phosphate buffer containing 16 % acetonitrile as running buffer），polyoxin B was separated within 4 min，and the ECL intensity was in proportion to logarithm of polyoxin B concentration over the range of 1.0×10-4-5.0×10-4 g/L and 5.0×10-4-5.0×10-2 g/L with a detection limit(3σ) of 9.2×10-5 g/L.The relative standard deviations（RSDs） of intra day and inter day ECL intensity and migration time were all less than 5.0%.The proposed method was successfully applied in the determination of polyoxin B absorbed in three kinds of soils（egbentonite，kaolinite and loess） with the recoveries of 92%-104%.The results also showed that the adsorption rate of polyoxin B in soils for 2 h was 89.0% for bentonite，45.5% for kaolinite and 40.4% for loess，respectively，indicating that the adsorption capacity of polyoxin B in different soils was bentonite>kaolinite>loess.The possible reason was related to the characteristics，specific surface area and cation exchange capacity（CEC） of soils.