The　rational　design　of　crystalline　clusters　with　adjustable　compositions　and　dimensions　is　highly　sought　after　but　quite　challenging　as　it　is　important　to　understand　their　structural　evolution　processes　and　to　systematically　establish　structure-property　relationships.　Herein,　a　family　of　organotin-based　sulfidometalate　supertetrahedral　clusters　has　been　prepared　via　mixed　metal　and　organotin　strategies　at　low　temperatures　(60-120　°C).　By　engineering　the　metal　composition,　we　can　effectively　control　the　size　of　the　clusters,　which　ranges　from　8　to　35,　accompanied　by　variable　configurations:　P1-[(RSn)4M4S13],　T3-[(RSn)4In4M2S16]　(R　=　nbutyl-Bu　and　phenyl-Ph;　M　=　Cd,　Zn,　and　Mn),　T4-[(BuSn)4In13Cu3S31],　truncated　P2,　viz.　TP2-[(BuSn)6In10Cu6S31],　and　even　T5-[(BuSn)4In22Zn6Cu3S52],　all　of　which　are　the　largest　organometallic　supertetrahedral　clusters　known　to　date.　Of　note,　the　arylstannane　approach　plays　a　critical　role　in　regulating　the　peripheral　ligands　and　further　enriching　geometric　structures　of　the　supertetrahedral　clusters.　This　is　demonstrated　by　the　formation　of　tin-oxysulfide　clusters,　such　as　T3-[(RSn)4Sn6O4S16]　(R　=　Bu,　Ph,　and　benzyl　=　Be)　and　its　variants,　truncated　T3,　viz.,　TT3-[(BuSn)6Sn3O4S13]　and　augmented　T3,　viz.,　T3-[(Bu3SnS)4Sn6O4S16].　Especially,　two　extraordinary　truncated　clusters　break　the　tetrahedral　symmetry　observed　in　typical　supertetrahedral　clusters,　further　substantiating　the　advantages　offered　by　the　arylstannane　approach　in　expanding　cluster　chemistry.　These　organometallic　supertetrahedral　clusters　are　highly　soluble　and　stable　in　common　solvents.　Additionally,　they　have　tunable　third-order　nonlinear　optical　behaviors　by　controlling　the　size,　heterometallic　combination,　organic　modification,　and　intercluster　interaction.　©　2024　American　Chemical　Society