Abstract:　In　this　work,　the　synthesis,　characterization,　and　phosphorescent　properties　of　the　coordination　polymer,　{Ag3(dppy)2[μ-SCN]3}n　(1),　are　described.　X-ray　crystallography　showed　that　the　complex　forms　a　one-dimensional　infinite　zipper-like　chained　structure　linked　by　thiocyanate　as　the　bridging　ligand.　The　silver(I)　complex　exhibits　a　strong　sky-blue　phosphorescence　with　a　high　quantum　yield　of　70.2%　in　the　solid　state　at　ambient　temperature.　Additionally,　following　a　temperature　change　from　418　to　77 K,　the　complex　displays　a　remarkable　luminescent　thermochromic　property.　Graphic　abstract:　A　novel　1D　zipper-like　silver(I)　coordination　polymer　is　constructed　by　2-diphenylphosphinopyridine　and　thiocyanate.　It　exhibits　strong　sky-blue　phosphorescence　with　high　quantum　yield　of　70.2%　in　solid　state　at　ambient　temperature.　Furthermore,　its　reversible　thermochromism　is　demonstrated.[Figure　not　available:　see　fulltext.]　©　2021,　The　Author(s),　under　exclusive　licence　to　Springer　Nature　Switzerland　AG.