Abstract: Zinc oxide hexagonal tubular crystals were synthesized by direct microwave heating from ZnO powders within 5 min without any metal catalysts or transport agents. ZnO source materials were evaporated from the high-temperature zone in an enclosure, and crystals were grown on the self-source substrate in an appropriate condition. The ZnO vapor formed in the high-temperature zone can deposit and grow on the powders located in the low-temperature zone to form crystals. The scanning electron microscopy (SEM) reveals that these products are hexagonal tube crystals with 80 μm in diameter and 250 μm in length, having a well faceted end and side surface. A possible growth mechanism and the influence of reaction temperature on the formation of crystalline ZnO hexagonal tubes were presented. The photoluminescence (PL) exhibits strong ultraviolet emission at room temperature, indicating the potential applications in short-wave light-emitting photonic devices.