A novel nano crystalline Ag2O2-PbO2 film chemically modified electrode (CME) was prepared and the CME was characterized by X-ray diffractometer (XRD) and atomic force microscope (AFM). By chronoamperometry, the nano Ag2O2-PbO2 CME was used as bioelectrochemical sensor to determine the population of Escherichia coli (E. coli) in water. Compared with conventional methods, it is found that the technique we used is fast and convenient in counting E.coli.