Three new diorganotin(IV) derivatives of pyruvic acid picolinoacylhydrazone, {Me2Sn[(2‐C5H4N)CONHNC(CH3)COO]}2·MeOH(1), {nBu2Sn[(2‐C5H4N)CONHNC(CH3)COO]}2 (2), and {Ph2Sn[(2‐C5H4N)CONHNC(CH3)COO]}2 (3) were synthesized by the reaction of Me2SnCl2, nBu2SnCl2, and Ph2SnCl2 with pyruvic acid picolinoacylhydrazone, respectively in the presence of sodium ethoxide. The prepared compounds were characterized by elemental analysis, IR, and 1H, 13C, and 119Sn NMR spectroscopy. Compounds 1 and 2 were also characterized by X‐ray diffraction analysis, which revealed that the compounds have similar structures containing two‐center‐two‐ligand skeletons. Furthermore, weak but significant intermolecular hydrogen bonds assemble these compounds into 1D or 2D supramolecular frameworks.