A series of new organotin(IV) derivatives with 2,3,4,5-tetrafluorobenzoic acid: {[(2,3,4,5-F 4 C 6 HCO 2 )R 2 Sn] 2 O} 2 (R=Et 1, n-Bu 2, Ph 3), [R 2 Sn(O 2 CC 6 F 4 H) 2 ] n (R=n-Bu 4, Et 5, Ph 6), and Sn 2 R 4 (O 2 CC 6 F 4 H) 3 (OH) (R=Et 7, n-Bu 8, Ph 9), were synthesized by the reaction of diorganotin oxide and 2,3,4,5-tetrafluorobenzoic acid. All the complexes 1-9 have been characterized by elemental analysis, IR, 1 H, 13 C, 119 Sn NMR spectra. Among them complexes 2, 4, 8 were also characterized by X-ray crystallography diffraction analyses. The crystal structure of complex 2 exhibited a tetra-nuclear geometry with the Sn 2 O 2 symmetry core. Complex 4 formed a 1D helical double-chain structure through intermolecular O→Sn coordinating and completed a DNA-like assembly. Complex 8 revealed that the both Sn atoms were held together by hydroxide and acetate bridges, forming a chair-like six-membered ring. Moreover, the supramolecular structures of dimer, 1D chain or 2D network have been found in complexes 4 and 8 by intermolecular C–H⋯F weak hydrogen bond and non-bonded F⋯F or F⋯Sn interaction, which were highly effective in the assembly of supramolecular structures and could lead to the formation of complexes with fascinating topologies properties.