Cu2O hollow spheres with thin shells were synthesized using poly(vinylpyrrolidone) (PVP) as the template in deionized water. In this process, CuAc2.H2O was reduced by acerbic acid in the presence of PVP and sodium hydroxide. Techniques, including XRD, XPS, TEM and HRTEM were used to characterize the morphology, structure and composition of the as-prepared nanomaterials. The results revealed that the average diameter of polycrystalline Cu2O hollow spheres is about 200 nm, with the shells as thin as approximately 10 nm. The formation mechanism, of these hollow spheres was studied. Magnetic property of the sample demonstrates a paramagnetic behavior at 15 K, and it might be attributed to the hollow-sphere structure of the diamagnetic Cu2O.