Various α-GaOOH nanorods were synthesized through a microwave-assisted method at 80 °C. In the synthesis, Ga(NO3)3 was used as the gallium source, and urea, L-cysteine, and EDTA disodium salt were used as the additives. The thermal decomposition of the as-prepared α-GaOOH nanorods could selectively produce α-, β-, and ε-Ga2O3 nanorods. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and cathodoluminescence were used to characterize the resulting samples. On the basis of characterization results, the possible growth mechanisms of these various GaOOH nanorods were proposed. This study provides a controllable method to prepare various gallium oxyhydroxide and gallium oxide nanorods.