Three　novel　heterometallic　oxysulfide　clusters　with　different　coordination　small　organic　molecules　have　been　solvothermally　synthesized　and　structurally　characterized,　i.e.,　[(nBuSn)3La(DTT)3(DETA)(L)]　(nBuSn　=　n-butyltin;　DTT　=　1,4-dithiothreitol;　DETA　=　diethylenetriamine;　L　=　N,N-dimethylformamide　(DMF)　(1),　N-methyl　pyrrolidone　(NMP)　(2),　and　N-methyl　formanilide　(MFA)　(3)).　These　clusters　are　a　bowl-shaped　structure,　composed　of　a　central　DETA-coordinated　La3+　cation　fixed　in　the　triangle　ring,　[(nBuSn)3(DTT)3],　and　an　amide　molecule　bonded　to　La3+　confined　inside　the　bowl.　The　coordinated　amides　can　be　changed　and　served　as　a　molecular　regulator　to　optimize　the　microsteric　interaction　between　the　clusters　and　further　the　physicochemical　property.　Remarkably,　the　crystals　of　1　exhibit　strong　blue-violet　light　emission　with　the　photoluminescence　quantum　yield　(PLQY)　of　3.69%,　which　significantly　exceeds　than　that　of　2　and　3　and　most　of　the　other　organotin　oxysulfide　clusters.　Theoretical　calculations　and　Hirshfeld　surface　analyses　indicate　that　the　weak　amide-oriented　intercluster　interactions　of　the　compounds　can　regulate　their　photoluminescence　(PL)　efficiency.　This　work　provides　a　paradigm　to　reveal　the　relationships　between　its　PL　and　structurally　fine-tuned　coordination　species.　©　2023　American　Chemical　Society.