Hydrothermal reaction of trimethyltin chloride with 1,2,4,5‐benzenetetracarboxylic acid (H4L1), 2,3‐pyridinedicarboxylic acid (H2L2) or 1,4,5,8‐naphthalenetetracarboxylic acid 4,5‐anhydride (H2L3) under optimized pH (5–6) and temperature (130 °C) results in the isolation of new dicarboxylatotetramethyldistannoxane‐based two‐/three‐dimensional coordination assemblies, [{Me2Sn(L1)0.25}2O] (1, 2 as supramolecular isomers), [{Me2Sn(L2)0.5}2O] (3) and [{Me2Sn(L3)0.5}2O] (4). The reaction in each case proceeds with selective cleavage of Sn–C bond. Analogous reaction of trimethyltin chloride with H4L1 at 100 °C affords [Me3Sn(L1)0.25] (5). The supramolecular coordination isomers 1 and 2 with cds and lvt network topologies, respectively are the first representatives among the distannoxane family; the latter confers large solvent accessible voids of 37 % per unit cell. The formation of ladder distannoxane, [{Me2Sn(O2C)}2O]2 as a common structural motif in 1, 3 and 4 is a manifestation of a predefined geometry of the inorganic secondary building unit (SBU) and follows the benchmark of reticular chemistry approach. The coordination assembly, 5 adopts an eight‐connected uninodal net that belongs to bcu topology. These are thermally stable up to 250–400 °C and retain their crystallinity even after exposure to hydrothermal treatment for 24 h.