Although　ionic　liquids　(ILs)　are　of　prime　interest　for　the　synthesis　of　various　nanomaterials,　they　are　scarcely　utilized　for　the　polyhydrido　copper(I)　[Cu(I)H]　clusters.　Herein,　two　air-stable　Cu(I)H　clusters,　[Cu8H6(dppy)6](NTf2)2　(Cu8H6)　and　{Cu12H9(dppy)6[N(CN)2]3}　(Cu12H9),　are　synthesized　in　high　yields　for　the　first　time　from　the　ILs-driven　conversion　of　an　unprecedented　cluster　[Cu7H5(dppy)6](ClO4)2　(Cu7H5)　by　a　facile　three-layers　diffusion　crystal　(TLDC)　method,　strategically　introducing　IL-NTf2　and　IL-N(CN)2　as　two　types　of　unusual　interfacial　crystallized　templates,　respectively.　Their　structures　are　fully　characterized　by　various　spectroscopic　methods　and　X-ray　crystallography,　which　shows　that　the　anion　of　IL　plays　an　important　role　as　an　anion　template　and　an　anion　ligand　in　controlling　the　structural　conversion　of　Cu(I)H　clusters.　Their　photophysical　properties　are　also　investigated,　and　it　is　found　that　all　reported　clusters　exhibit　red　luminescence　with　λem　ranging　from　600　to　690　nm.　©　2023　American　Chemical　Society