Bi2WO6/BN heterojunction photocatalyst with high catalytic activity has been successfully constructed by the solvothermal synthesis. It is worth noting that the formation of superoxide radicals (·O2-) and hydroxyl free radicals (·OH) benefit from the formation of heterojunctions, which effectively degrade pollutants. The photocatalytic activities of the optimal sample for tetracycline (TC) and ofloxacin (OFL) degradation efficiency reached almost 99.1% and 94.66% under visible-light irradiation, respectively. It is mainly because the addition of BN not only provided more active sites for the catalyst but also improved the separation efficiency of electron-hole pairs. It can be found that h+ and·O2- played a major role in the degradation process through the active species quenching experiment. Furthermore, the possible photocatalytic degradation pathways of TC were revealed by analyzing intermediates and a reasonable photocatalytic mechanism was proposed. Moreover, Bi2WO6/BN heterojunctions were endowed with excellent recycling and stability. Therefore, this research illustrated that two dimensions/two dimensions (2D/2D) Bi2WO6/BN heterojunction may hold a great prospect for the degradation of antibiotics in wastewater.