Surface junctions between Bi OBr and BiVO_4 were synthesized. The BiOBr/BiVO_4 with 1 wt.%of Bi OBr exhibited the highest photocatalytic activity in the degradation of Rh B under visible-light irradiation. It was found that the highly efficient adsorption of Rh B molecules via the electrostatic attraction between Br-and cationic N(Et)_2 group played a key role for the high photocatalytic activities of BiOBr/BiVO_4. This efficient adsorption promoted the N-deethylation of Rh B and thus accelerated the photocatalytic degradation of Rh B.Moreover, the metal-to-metal charge transfer(MMCT) mechanism was proposed, which revealed the concrete path paved with Bi–O–Bi chains for the carrier migration in BiOBr/BiVO_4. The interaction between photoexcited Rh B* and the Bi~(3+) in BiVO_4 provided the driving force for the migration of photo-generated carriers along the Bi–O–Bi chains. This work has not only demonstrated the important role of efficient adsorption in the photocatalytic degradation of organic contaminants, but also developed a facile strategy to improve the efficiency of photocatalysts. The junctions between Bi OBr and BiVO_4 were synthesized. The BiOBr / BiVO_4 with 1 wt.% Of Bi OBr presents the highest photocatalytic activity in the degradation of Rh B under visible-light irradiation. It was found that the highly efficient adsorption of Rh B molecules via the electrostatic attraction between Br-and cationic N (Et) _2 group played a key role for the high photocatalytic activities of BiOBr / BiVO_4. This efficient adsorption promoted N-deethylation of Rh B and thus accelerated the photocatalytic degradation of Rh B. Moreover, the metal-to-metal charge transfer (MMCT) mechanism was proposed, which revealed the concrete path paved with Bi-O-Bi chains for the carrier migration in BiOBr / BiVO_4. The interaction between photoexcited Rh B * and the work of the Bi ~ (3+) in BiVO_4 provided the driving force for the migration of photo-generated carriers along the Bi-O-Bi chains. This work has not only demonstrated the important role of efficient adsorption in the photocatalytic deg radation of organic contaminants, but also developed a facile strategy to improve the efficiency of photocatalysts.