Controlling　excited-state　dynamics　is　crucial　for　achieving　dual　emissions　of　ultralong　room-temperature　phosphorescence　(URTP)　and　thermally　activated　delayed　fluorescence　(TADF),　but　remains　challenging　in　the　exploration　of　transition-metal　compounds.　Herein,　we　propose　a　new　strategy　to　develop　highly　efficient　TADF　and　URTP　dual-emission　materials　by　modulating　URTP　organic　molecules　through　metal　ion　coordination.　Specifically,　Ag+　ions　narrow　the　singlet-triplet　energy　gap　(ΔEST)　and　enhance　spin-orbit　coupling　(SOC),　thereby　accelerating　intersystem　crossing　(ISC)　and　facilitating　reverse　intersystem　crossing　(RISC).　The　Ag+　ions　also　balance　radiative　transitions　and　RISC　processes　of　the　T1　state.　Consequently,　coordinating　the　URTP　molecule　Phen-Tpa　with　Ag+　ions　results　in　an　Ag(i)　complex　that　exhibits　efficient　ligand-centered　TADF　and　URTP　dual　emissions　in　MeOBP　films,　with　a　quantum　yield　of　85%,　an　afterglow　duration　of　6　seconds,　and　a　record　long　emission　lifetime　of　575.7　ms.　Moreover,　Phen-Tpa　can　be　used　to　fabricate　organic　white　light-emitting　diodes　(LEDs),　while　both　Phen-Tpa　and　the　Ag(i)　complex　offer　high-security　anti-counterfeiting　capabilities.　These　results　deepen　the　understanding　of　how　metal　fragment　coordination　influences　luminescence　mechanisms　and　provide　a　new　approach　for　achieving　dual　emissions　with　coexisting　TADF　and　URTP　in　transition-metal　compounds.　©　2025　The　Royal　Society　of　Chemistry.