Zinc complexes with the mixed scorpionate ligand (6‐tert‐butyl‐3‐thiopyridazinyl)bis(2‐thiomethimidazolyl)borate (PnBm) have been synthesized and characterized by NMR and IR spectroscopy. The complexes, with the general formula [(PnBm)ZnX]2 [X = Br (1a), I (1b)], are dimeric in the solid state, as determined by single‐crystal X‐ray diffraction analyses. The zinc atoms are tetrahedrally coordinated by the halogen atom, two sulfur atoms of PnBm, and one sulfur atom from a bridging PnBm ligand. Variable‐temperature 1H NMR spectroscopy indicated dimeric structures also in solution. Upon abstraction of the bromine atom in 1a by thallium triflate, the zinc complex [(PnBm)Zn(OTf)]2 (2) was obtained and fully characterized by 1H and 13C NMR spectroscopy, elemental analysis, and single‐crystal X‐ray diffraction analysis.