A cubic Prussian blue (PB) with the hollow interior was successfully synthesized by direct dissociation followed by a controlled self-etching process. The etching process also made hollow Prussian blue (HPB) a porous structure. SEM, TEM and XRD were employed to confirm the structure and morphology of the prepared materials. Then HPB and chitosan (CS) were deposited on a glassy carbon electrode (GCE), used to determine H2O2. The amperometric performance of HPB/CS/GCE was investigated. It was found that the special structure of HPB exhibits enhanced performance in the H2O2 sensing.