The seleno- and tellurostannate(IV) anions Sn2Ch6 4- and Sn2Ch7 4- (Ch = Se, Te) have been obtained by extraction of the ternary alloys KSn0.67Se1.93 and KSn0.63Te1.70 in ethylenediamine (en) and/or liquid NH3 in the absence and in the presence of nonstoichiometric amounts of 2,2,2-crypt (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) with respect to K+. The anions were characterized in solution for the first time by natural abundance 77Se, 119Sn, and 125Te NMR spectroscopy. The magnitudes of the relativistically corrected reduced coupling constants 1 K(Sn−Cht)RC, 1 K(Sn−Chmb)RC, and 1 K(Sn−Chdb)RC were shown to be consistent with a significant degree of s-character in the bonding. The Sn−Chmb and Sn−Cht bond distances observed for the dimeric SnCh3 2- anions, namely Sn2Ch6 4-, in K+(N(CH3)4 +)3Sn2Se6 4- (1), (enH+)2(2,2,2-crypt-K+)2Sn2Se6 4- (2), and (K+)2(2,2,2-crypt-K+)2Sn2Te6 4- (3) were shown to correlate with the 1 K(Sn−Ch)RC values, indicating that the solid-state molecular structures of the anions are retained in solution. The Raman spectra of compounds 1−3 are also reported along with their respective factor-group analyses. The novel HOSnTe3 3- anion, the hydroxide derivative of the SnTe3 2- anion, has been structurally characterized by X-ray crystallography in K+(2,2,2-crypt-K+)2HOSnTe3 3- (4) and in K+(2,2,2-crypt-K+)2HOSnTe3 3-·en (5) and represents the first example of a simple mixed hydroxychalcogenide anion of tin.