Al₂O₃ nanorods with mesoporous structures are successfully synthesized from a hydrothermal and thermal decomposition process via the ammonium aluminum carbonate hydroxide (denoted as AACH) precursors. TEM images show that the average diameter of Al₂O₃ nanorods is about 60 nm, and the length is around 1–2 μm. The experimental results show that well-crystallized mesopores with hierarchically distributed pore sizes are embedded in the Al₂O₃ nanorods. The N₂ adsorption–desorption experiment indicates that the as-synthesized alumina nanorods have large surface area (ca. 176 m²/g) and narrow pore-size distributions. At the same time, the as-prepared Al₂O₃ nanorods exhibit strong photoluminescent properties at room temperature. A plausible surfactant-induced nanorod formation mechanism using the poly ethylene glycols as the template agent for the nanorod assembly is also proposed.