Phosphorus-doped (P-doped) TiO2 catalysts with a stable anatase-brookite biphase structure were successfully synthesized by integrating ultrasonication with phosphorus doping and Pluronic P123 surfactant. The synthesized catalysts were characterized using X-ray diffraction, transmission electron microscopy, nitrogen adsorption-desorption, Fourier transform infrared, and UV-visible diffuse reflectance spectra. Ultrasonication facilitates the appearance of brookite phase. Phosphorus doping was demonstrated an effective strategy to stabilize the anatase-brookite biphase structure and inhibits undesirable grain growth. Triblock copolymer Pluronic P123 used in the reaction facilitates the formation of catalyst particles with mesoporous structure and large surface area and prevents particles from agglomeration. The low band-gap of brookite phase enables the synthesized P-doped TiO2 catalysts outperform commercial P25 TiO2 and N-doped TiO2 in the degradation of methylene blue under both solar light and visible light irradiation.