A series of tris(pentafluorophenyl)corrole (TPFC) tin(IV) and tin(II) complexes were prepared and studied by various characterization techniques including (1)H, (19)F, and (119)Sn NMR and UV-vis spectroscopy, mass spectrometry, and single-crystal X-ray diffraction. The unusual 4-coordinate, monomeric, divalent tin(II) complex [(TPFC)Sn(II)](-) (2a) showed highly efficient reactivity toward alkenes and alkyl halides via a nucleophilic addition pathway leading to the quantitative formation of alkyl stannyl corrole compounds. DFT calculations confirmed the divalent nature of the tin center in 2a, and an NBO analysis showed about 99.99% Sn lone pair character, of which 83.6% was Sn 5s and 16.35% was Sn 5p character.