Background:　The　realization　of　multifunction　in　one　bulk　material　is　fascinating　for　developing　a　new　generation　of　devices.　Quaternary　phosphorus　salts　were　seldom　utilized　as　templates　in　haloargentate　systems,　and　the　hybridization　of　alkyl(triphenyl)phosphonium　with　halometallate　will　be　a　good　strategy　for　the　development　of　multifunctional　material,　especially　for　biological　material.　Methods:　Under　the　template　of　(triphenyl)phosphonium-based　quaternary　phosphorus　salts　with　different　spacer　lengths　(n=2,　3,　4),　three　bromoargentate　hybrids　were　constructed　via　the　solution　method,　ie,　(1,2-DBTPP)(Ag2Br4)　(1),　{(1,3-DBTPP)2(Ag7Br11)]∙CH3CN∙H2O}n　(2),　and　{[(1,4-DBTPP)(Ag5Br7)](CH3CN)2∙H2O}n　(3)　(1,2-DBTPP2+=ethane-1,2-diylbis　(triphe-nyl)phosphonium,　1,3-DBTPP2+=propane-1,3-diylbis　(triphenyl)phosphonium,　1,4-DBTPP2　+=butane-1,4-diylbis　(triphenyl)phosphonium)).　Results:　The　(Ag7Br11)n4n-chain　in　2　is　a　new　type　of　1-D　bromoargentate　chain　constructed　from　cubane-like　Ag4Br4　nodes,　AgBr4　tetrahedrons　and　AgBr3　triangles.　Interestingly,　by　elongating　spacer　n　from　2　to　4,　argentophilicity　interactions　are　weakened,　and　the　hydrogen　bonds　are　strengthened.　Consequently,　their　water　stabilities　and　photocurrents　are　improved,　in　which　the　Ag-4d/Br-4p　to　π*　anti-bonding　orbital　of　the　quaternary　phosphorus　transfer　is　facilitated.　Furthermore,　the　greenish　blue　emissions　can　be　detected.　Finally,　high　inhabita-tion　rates　against　Streptococcus　mutans　and　Candida　albicans　can　be　observed　in　2　and　3.　Conclusion:　In　all　experiments,　by　elongating　the　spacer　lengths　of　quaternary　phosphorus　salts,　multifunctions　were　integrated　in　the　quaternary　phosphorus/bromoargentate　hybrids,　including　greenish　blue　luminescence,　repeatable　photocurrent　responses　and　durable　anti-microbial　activities　with　enhanced　water　stability.　This　work　could　provide　a　theoretical　guide　for　the　design　of　new　biologically　multifunctional　materials.　©　2020　Liu　et　al.