A new dibutyltin(IV) carboxylate with 2‐(4‐ethylbenzoyl)benzoic acid (HL), {[n‐Bu2Sn(L)]2O}2, (1) was synthesized and characterized by elemental analysis, IR, 1H, 13C, 119Sn NMR spectroscopy. X‐ray crystallography diffraction analysis shows 1 is a centrosymmetric tetranuclear tetrabutyldistannoxane complex containing a planar Sn4O2 core in which two μ3‐oxygens connect a Sn2O2 ring to two exocyclic Sn atoms. The four carboxyl groups display two different modes of coordination: monodentate and bidentate coordination. The molecules of 1 build 1D chain structure and 2D network supramolecular structure through intermolecular hydrogen bonds. The luminescent property of 1 was preliminarily studied.