Oxidation behavior of Cu nanoparticles in the formation process of hollow Cu2O spheres was investigated by TEM. The thickness of Cu2O layers on Cu nanoparticles oxidized at 323 K in air was measured as a function of oxidation time. At the initial stage of oxidation until the oxide film with 2.5 nm in thickness is formed, the thickness of oxide films on Cu nanoparticles with the diameter of 10, 20 and 35 nm shows a nearly equal value regardless of diameter of Cu. After the formation of 2.5 nm layer, however, the growth rate of the oxide films on smaller nanoparticles becomes slower than that on larger nanoparticles. This result suggests that the voids formed at the Cu/Cu2O interface prevent Cu atoms from diffusing outward across the interface because the volume ratio of voids to inner Cu in smaller nanoparticles is much larger than that in larger nanoparticles.