Discrete　supertetrahedral　Tn　chalcogenido　clusters,　which　can　be　regarded　as　the　smallest　semiconductor　quantum　dots　with　precise　chemical　composition,　have　attracted　considerable　attention　due　to　their　outstanding　photoluminescent,　photoelectric,　and　photo/electrocatalytic　properties.　Such　discrete　molecular　clusters　are　suitable　for　solution　processing　towards　functional　materials　and　can　be　used　as　precursors　for　constructing　open-framework　chalcogenides.　Traditionally　they　were　synthesized　hydro(solvo)thermally　with　molecular　solvents　(e.　g.　water　or　organic　amines),　while　until　recently　imidazolium-based　ionic　liquids　(ILs)　were　found　suitable　for　their　preparation　acting　as　reactive　solvent　and　stabilizer　for　molecular　clusters.　We　discuss　herein　recent　advances　in　the　syntheses,　crystal　structures,　and　selected　properties　of　discrete　supertetrahedral　Tn　chalcogenido　clusters　obtained　in　ILs.　In　particular,　the　enhanced　photocatalytic　properties　of　monodispersed　Tn　clusters　in　solvents　are　highlighted.