Phosphonium montmorillonites (P-MMTs) were prepared by intercalating dodecyl tributyl phosphonium salt into sodium montmorillonite (Na-MMT) through an ion-exchange method. Microstructure and antibacterial activity of phosphonium montmorillonites were studied by FT-IR, TGA, XRD and Minimum Inhibitory Concentration (MIC), respectively. The results show that phosphonium montmorillonites exhibit higher thermal stability than conventional ammonium montmorillonites, the onset temperature of decomposition is higher than 300 $^{circ}C$, and the basal spacing of phosphonium montmorillonites is enlarged compared to that of sodium montmorillonite. Phosphonium montmorillonites also show good antibacterial activity with the MIC against E. coli and S. aureus of 150 and 50 $mg{cdot}L^{-1}$, respectively.