Bowl-like ZnO nanostructures with hexagonal shape have been fabricated by a solvent-thermal synthesis route with the assistance of ultrathin anodic aluminum oxide (AAO) template. Transmission electron microscopy and high-resolution transmission electron microscopy investigations confirm that the bowllike ZnO structures are single-crystalline. The room temperature photoluminescence investigation shows that the products have a sharp near band-edge emission and another broad green emission band centered at 386 nm and around 525 mn, respectively.