Pt/polypyrrole (PPy) hybrid hollow microspheres were successfully prepared by wet chemical method via Fe(3)O(4) template and evaluated as electrocatalysts for the reduction of hydrogen peroxide. The as-synthesized products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), X-ray diffraction (XRD), inductive coupled plasma emission spectrum (ICP) and Fourier-transform infrared spectra (FTIR) measurements. The results exhibited that ultra-high-density Pt nanoparticles (NPs) were well deposited on the PPy shell with the mean diameters of around 4.1nm. Cyclic voltammetry (CV) results demonstrated that Pt/PPy hybrid hollow microspheres, as enzyme-less catalysts, exhibited good electrocatalytic activity towards the reduction of hydrogen peroxide in 0.1M phosphate buffer solution (pH=7.0). The composite had a fast response of less than 2s with linear range of 1.0-8.0mM and a relatively low detection limit of 1.2microM (S/N=3). The sensitivity of the sensor for H(2)O(2) was 80.4mAM(-1)cm(-2).