Novel Biomass carbon modified Bi2WO6 with 3D flower-like nanostructures were firstly fabricated through a hybridization approach, and investigated by multiple techniques including XRD, XPS, SEM and TEM analysis, etc. Compared with the pristine Bi2WO6, Bi2WO6/C hybrids exhibit higher visible-light photocatalytic activity and stability for tetracycline (TC) photodegradation. Moreover, the obviously enhanced photodegradation performance of Bi2WO6/C hybrids was mainly attributed to the modification of biomass carbon with good natures in specific surface area, narrow band gap (2.51 eV) and electronic transmission, which greatly improved the adsorption capacity and facilitated the separation of charge carriers. Furthermore, a possible photocatalytic mechanism of Bi2WO6/C hybrids in the view of active radicals has been discussed, which was also ascribed to the outstanding degraded ability of the ·OH evolved from the supersaturated ·O2− through trapping and ESR experiments. More importantly, these findings provide new insights to the utilization of biomass carbon modified other Bi-based photocatalysts and enhancing the photocatalytic performance to address environmental problems.