beta-Ga2O3 nanorod array clumps were successfully synthesized on Si (111) substrates by chemical vapor deposition. The composition, microstructure, morphology, and light-emitting property of these clumps were characterized by X-ray diffraction, Fourier transform infrared spectrophotometry, X-ray photoelectron spectroscopy, scanning electron microscopy, high-resolution transmission electron microscopy, Raman spectroscopy, and photoluminescence. The results demonstrate that the sample synthesized at 1050 degrees C for 15 min was composed of monoclinic beta-Ga2O3 nanorod array clumps, where each single nanorod was about 300 nm in diameter with some nano-droplets on its tip. These results reveal that the growth mechanism agrees with the vapor-liquid-solid (VLS) process. The photoluminescence spectrum shows that the Ga2O3 nanorods have a blue emission at 438 nm, which may be attributed to defects, such as oxygen vacancies and gallium-oxygen vacancy pairs. Defect-energy aggregation confinement growth theory was proposed to explain the growth mechanism of Ga2O3 nanorod array clumps collaborated with the VLS mechanism.