Nano titanium dioxide (TiO₂) with photocatalytic activity was firstly modified by diethanolamine, and it was then doped with broad spectrum antibacterial silver (Ag) by in situ method. Further, both Ag doped TiO₂-chitosan (STC) and TiO₂-chitosan (TC) composites were prepared by the inverse emulsion cross-linking reaction. The antibacterial activities of STC composites were studied and their antibacterial mechanisms under visible light were investigated. The results show that in situ doping and inverse emulsion method led to good dispersion of Ag and TiO₂ nanoparticles on the cross-linked chitosan microsphere. The STC with regular particle size of 1–10 μm exhibited excellent antibacterial activity against E. coli, P. aeruginosa and S. aureus under visible light. It is believed that STC with particle size of 1–10 μm has large specific surface area to contact with bacterial cell wall. The increased antibacterial activity was attributed to the enhancement of both electron-hole separations at the surface of nano-TiO₂ by the silver ions under the visible light, and the synergetic and sustained release of strong oxidizing hydroxyl radicals of nano-TiO₂, together with silver ions against bacteria. Thus, STC composites have great potential applications as antibacterial agents in the water treatment field.