An in‐depth investigation was conducted on a promising composite material (BiVO4/TiO2), focusing on its potential toxicity, photoinduced catalytic properties, as well as its antibiofilm and antimicrobial functionalities. The preparation process involved the synthesis of 2D‐TiO2 using the lyophilization method, which was subsequently functionalized with sphere‐like BiVO4. Finally, we developed BiVO4/TiO2 S‐scheme heterojunctions which can greatly promote the separation of electron‐hole pairs to achieve high photocatalytic performance. The evaluation of concentration‐ and time‐dependent viability inhibition was performed on human lung carcinoma epithelial A549 cells. This assessment included the estimation of glutathione levels and mitochondrial dehydrogenase activity. Significantly, the BiVO4/TiO2 composite demonstrated minimal toxicity towards A549 cells. Impressively, the BiVO4/TiO2 composite exhibited notable photocatalytic performance in the degradation of rhodamine B (k =0.135 min‐1) and phenol (k = 0.016 min‐1). In terms of photoinduced antimicrobial performance, the composite effectively inactivated both gram‐negative E. coli and gram‐positive E. faecalis bacteria upon 60‐min of UV‐A light exposure, resulting in a significant log6(log10CFU/mL) reduction in bacterial count. These promising results can be attributed to the unique 2D morphology of TiO2 modified by sphere‐like BiVO4, leading to an increased generation of (intracellular)hydroxyl radicals, which plays a crucial role in treatments of both organic pollutants and bacteria.