Ga2O3 nano-structures, nanowires and nanosheets are produced on Au pre-coated(111) silicon substrates with chemical vapor deposition(CVD) technique. By evaporating pure Ga powder in the H-O atmosphere under ambient pressure the large-scale preparation ofβ-Ga2O3with monoclinic crystalline structure is achieved. The crystalline structures and morphologies of produced Ga2O3nano-structures are characterized by means of scanning electron microscope(SEM), X-ray diffraction(XRD), selected area electron diffraction (SAED) and transmission electron microscope(TEM). Raman spectrum reveals the typical vibration modes of Ga2O3. The vibration mode shifts corresponding to Ga2O3nano-structures are not found. Two distinguish photoluminescence(PL) emissions are found at about 399 nm and 469 nm owing to the VO2VGaexcitation and VO2VGa2Oexcitation, respectively. The growth mechanisms of Ga2O3nanowires and nanosheets are discussed with vapor-liquid-solid(VLS) and vapor-solid(VS) mechanisms.