A new bleaching agent consisting of a titanium dioxide photocatalyst and 3.5% hydrogen peroxide has recently been developed for in-office bleaching and has proven to react well with irradiated light around a wavelength of 400 nm. This study was conducted to evaluate the efficacy of dental bleaching with a 405-nm diode laser irradiation on titanium dioxide and 3.5% hydrogen peroxide by measuring the generation of hydroxyl radicals. The amount of hydroxyl radicals generated from a titanium dioxide and 3.5% hydrogen peroxide irradiated by a 405-nm diode laser were measured using electron spin resonance spin-trapping techniques. The irradiation conditions of the laser were a spot size of 1 mm, output powers of 100, 200, 400 mW, and 600 mW, and irradiation times of 10, 20, 30, and 60 s. Nonirradiated samples were used as controls. DMPO-OH adduct spectra and DMPO-O-2(-) adduct spectra were observed when the bleaching agent was irradiated by laser light. The amount of hydroxyl radicals generated changed in accordance with adjustments in the irradiation power and irradiation time. In the nonirradiated controls, hydroxyl radicals were generated in far smaller amounts. The 405-nm diode laser is effective in inducing the generation of hydroxyl radicals and shows promise as a bleaching light source for use in combination with bleaching agents composed of titanium dioxide and low concentrations of hydrogen peroxide.