The synthesis and characterization of a series of Sn(ii) and Sn(iv) complexes supported by the highly electron-withdrawing dianionic perfluoropinacolate (pinF) ligand are reported herein. Three analogs of [SnIV(pinF)3]2- with NEt3H+ (1), K+ (2), and {K(18C6)}+ (3) counter cations and two analogs of [SnII(pinF)2]2- with K+ (4) and {K(15C5)2}+ (5) counter cations were prepared and characterized by standard analytical methods, single-crystal X-ray diffraction, and 119Sn Mössbauer and NMR spectroscopies. The six-coordinate SnIV(pinF) complexes display 119Sn NMR resonances and 119Sn Mössbauer spectra similar to SnO2 (cassiterite). In contrast, the four-coordinate SnII(pinF) complexes, featuring a stereochemically-active lone pair, possess low 119Sn NMR chemical shifts and relatively high quadrupolar splitting. Furthermore, the Sn(ii) complexes are unreactive towards both Lewis bases (pyridine, NEt3) and acids (BX3, Et3NH+). Calculations confirm that the Sn(ii) lone pair is localized within the 5s orbital and reveal that the Sn 5px LUMO is energetically inaccessible, which effectively abates reactivity.