Partially filled ZnO microtubes were synthesized in large scale using block copolymers. The growth mechanism of this unique construction is proposed on the basis of adsorption of block copolymers on {0002} plane of wurtzite ZnO. The photoluminescence property of these unique ZnO microtubes is also studied using a Xe lamp as the excitation source at room temperature. Blue emission band at 425 run is a much stronger ultraviolet emission band, which is due to laminar structure of ZnO microtubes.