The morphological and structural evolution is presented for GaN nanorods grown by chemical beam epitaxy on (0001) Al2O3 substrates. Their structural and optical properties are investigated by x-ray diffraction, scanning and transmission electron microscopy, and temperature-dependent photoluminescence measurements. While increasing the growth temperature and the flow rate of radio-frequency nitrogen radical, the three-dimensional growth mode will be enhanced to form one-dimensional nanostructures. The high density of well-aligned nanorods with a diameter of 30-50 nm formed uniformly over the entire sapphire substrate. The x-ray diffraction patterns and transmission electron microscopic images indicate that the self-assembled GaN nanorods are a pure single crystal and preferentially oriented in the c-axis direction. Particularly, the "S-shape" behavior with localization of similar to 10 meV observed in the temperature-dependent photoluminescence might be ascribed to the fluctuation in crystallographic defects and composition.