Possessing active sites, tunable band gaps and short charge transfer paths, 2D/2D heterojunctions with face-to-face contact are considered to be one kind of promising photocatalysts. Herein, typical 2D/2D structured BiYO3/BiOBr photocatalysts have been fabricated via an electrostatic self-assembly route. When used to degrade Congo red, the heterogeneous composite with the mass ratio of BiYO3 to BiOBr as 1:1 exhibits the highest photocatalytic degradation efficiency and kinetic rate respectively of 90.14 % and 0.0108 min−1. In addition, it demonstrates excellent performance in degrading other organic pollutants, as the removal efficiencies can attain 97.25 % (Rhodamine B), 96.03 % (malachite green) and 99.05 % (butyl xanthate), respectively. Electrochemical and photoluminescence results indicate that BiYO3 and BiOBr can combine well to form a heterojunction structure to inhibit the recombination of photogenerated electron-hole pairs and improve the transport efficiency. The results of energy band structure analysis, trapping experiment and electron spin resonance (ESR) confirm the formation of Z-scheme heterojunction between BiYO3 and BiOB rather than type II ones.