A new ［BMIM］PF6-MnO2-CHIT/GCE modified electrode was fabricated via the chitosan（CHIT） filming using hydrophobic ionic liquid 1 butyl 3 methylimidazolium hexafluorophosphate（［BMIM］PF6） and nano MnO2 as modifiers.In Britton-Robinson（B-R） buffer，the electrochemical behavior of baicalin at ［BMIM］PF6-MnO2-CHIT/GCE was studied，and a new method for the determination of baicalin in radix scutellariae was developed.The cyclic voltammetry curves of baicalin at ［BMIM］PF6-MnO2-CHIT/GCE presented a pair of sensitive and reversible redox peaks.The peak current responsed at the proposed electrode was enhanced 26 folds higher than that at the MnO2-CHIT/GCE，and the peak potential difference was 0062 V，the electron transfer rate constant ks was 0258 s-1.The change of the oxidation peak current with baicalin concentration at ［BMIM］PF6-MnO2-CHIT/GCE was examined by differential pulse voltammetry.The calibration curve was linear in the concentration range of 10×10-9-10×10-5 mol/L with a detection limit（S/N=3） of 10×10-10 mol/L.The relative standard deviation（n=5） of 10×10-8 mol/L baicalin was 21%.The method was applied in the determination of baicalin in samples with satisfactory results，and the spiked recoveries were in the range of 95%-103%.