Mesoporous wide bandgap semiconductors offer high photocatalytic oxidation and mineralization activities. In this study, mesoporous β-Ga(2)O(3) diamond nanorods with 200-300 nm in diameter and 1.0-1.2 μm in length were synthesized via a urea-based hydrothermal method using polyethylene glycol (PEG) as template agent. The UV photocatalytic oxidation activity of β-Ga(2)O(3) for gaseous toluene was evaluated, and 7 kinds of intermediates were monitored online by a proton transfer reaction mass spectrometry. Photoluminescence spectra manifested that the dosage and molecular weight of PEG are crucial for formation of vacancies and photocatalytic oxidation activities. A PEG-assisted hydrothermal formation mechanism of mesoporous β-Ga(2)O(3) diamond nanorods was proposed. Based on the health risk influence index (η) of the intermediates, the calculated health risks revealed that the β-Ga(2)O(3) nanorods with a η value of 9.6 are much safer than TiO(2) (η = 17.6).