Triplet-state-based　luminescence　holds　great　promise　for　next-generation　optoelectronic　materials,　yet　its　mechanistic　modulation　through　structural　control　remains　a　fundamental　challenge　for　nanomaterials.　Here,　we　present　a　comparative　study　of　two　atomically　precise　nanoclusters,　Au6Ag2　and　Au6Ag4,　which　feature　an　identical　Au6　core　but　differ　subtly　in　Ag　atom　count　and　ligand　coordination.　Despite　their　structural　similarity　and　triplet　dominated　emission　origin,　the　results　herein　reveal　that　Au6Ag2　exhibits　phosphorescence,　whereas　Au6Ag4　demonstrates　dual　emission　involving　both　phosphorescence　and　thermally　activated　delayed　fluorescence　(TADF).　The　contrasting　behaviors　arise　from　fine-tuning　the　silver　contents　and　organic　ligands,　which　alters　photoluminescence　nature　without　modifying　the　metal　core.　This　work　highlights　a　structure-driven　approach　to　regulating　triplet-state　photoluminescence　in　metal　nanoclusters　and　offers　a　blueprint　for　designing　next-generation　triplet-emissive　materials.