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)]center　dot　CH3CN　center　dot　H2O}(n),　(2),　and　[(1,4-DBTPP)(Ag5Br7)](CH3CN)(2)center　dot　H2O}(n),　(3)　(1,2-DBTPP2+=ethane-1,2-diylbis　(triphenyl)phosphonium,　1,3-DBTPP2+=propane-1,3-diylbis　(triphenyl)phosphonium,　1,4-DBTPP2+　=butane-1,4-diylbis　(triphenyl)phosphonium)).　Results:　The　(Ag7Br11)(n)(4n-)　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　pi*　anti-bonding　orbital　of　the　quaternary　phosphorus　transfer　is　facilitated.　Furthermore,　the　greenish　blue　emissions　can　be　detected.　Finally,　high　inhabitation　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　antimicrobial　activities　with　enhanced　water　stability.　This　work　could　provide　a　theoretical　guide　for　the　design　of　new　biologically　multifunctional　materials.