A phase junction over a Bi(2)SiO(5) photocatalyst with the orthorhombic Bi(2)SiO(5) and the tetragonal Bi(2)SiO(5) structure was successfully synthesized via an ion exchange method using BiOBr solid microspheres as the sacrificial template. In the meantime, the as-prepared Bi(2)SiO(5) phase junction possesses a novel morphology of a flower-like microsphere with nanoparticles evenly embedded in its nano-petals. It was found that the Bi(2)SiO(5) phase junction not only showed a highly enhanced photocatalytic activity and excellent durability under UV or simulated solar irradiation, but also showed a remarkable visible-light activity for photo-degradation of phenol. Experimental results reveal that the tetragonal Bi(2)SiO(5) phase in this phase junction possesses a narrower band gap, thus leading to its extended light absorption. The efficient charge separation via a phase junction would make a great contribution to its highly enhanced photocatalytic activity under UV or simulated solar irradiation. The high efficiency in the degradation of organic pollutants makes the as-prepared photocatalyst a promising candidate for photocatalytic environmental purification.