The polyaniline (PAn)/carbon black (CB) hybrid hollow microspheres have been prepared by the layer-by-layer assembly technique alternately adsorbing of PAn and CB onto the polystyrene sulfonate microsphere templates after etching the templates by dialysis. The hollow structure of the obtained hybrid hollow microspheres was characterized by transmission electron microscopy, which indicated that the external diameter of the hollow microspheres was about 3.0μm. When the hybrid hollow microsphere were used as the electrode material for supercapacitors, the results showed that the specific capacitance increased with the increase in the adsorption numbers of PAn and CB, which was as high as 532Fg−1 at a charge–discharge current density of 10mAcm−2 in 1.0M H2SO4 electrolyte after alternately adsorbing of PAn and CB six times.