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Na-montruorillonite (Na-MMT) was exchanged with three quatary alkylphosphonium salts:decyl tributylphosphonium bromide (DTBPBr), dodecyl tributylphosphonium bromide (DDTBPBr) and hexadecyl tributylphosphonium bromide (HDTBPBr), to investigate the effects of phosphonium salts species and relative molecular mass on the characteristics, morphology, thermal stability and long-acting antibacterial property of phosphonium montmorillonites. The resulting modified montmorillonites were characterized by the FTIR, XRD, TEM, and TG/DTG techniques. And minimum inhibitory concentration (MIC) was used to investigate antibacterial activity. The results show that the phosphonium salts are intercalated into Na-MMT, and the basal spacing of P-MMTs is enlarged with the increase of phosphonium salt content or the growth of alkyl chain length. DDTBP-MMT-3 with 19.83% (mass fraction) of dodecyl tributylphosphonium salts, displays excellent thermal stability and long-acting antibacterial activity.