A multi-wall carbon nanotube/poly L-histidine compound membrane electrode (MWCNTs/poly-L-HiS/GCE) is prepared by polymerizing L-histidine to a glass carbon electrode and then dropping a multi-walled carbon nanotube suspension liquid to poly-L-HiS/CGE. In a PBS buffer solution, the pH of which is 7.0, an electrochemical behavior of hydroquinone (HQ) on a modified electrode is researched by virtue of cyclic voltammetry, and the property thereof is represented by means of electrochemical impedance spectroscopy (EIS), influence on hydroquinone determination by sweep rate, pH and etc. are discussed, the experimental condition is optimized, and finally, the HQ solutions with different concentrations are determined by means of differential pulse voltammetry (DPV). Experimental results verify that the response current on a composite electrode of HQ is obviously enhanced, and a good linear relationship with an oxidation peak current (Ipa) in a concentration range of 5.0*10<-8>-8*10<-4>mol/L is shown. The coefficient of association is 0.998, and when the signal to noise ratio is 3, the detection limit is 1.0*10<-8>mol/L.