The complex Sn(II) fluorides ASnF 3 (A = Na, K, Rb, Cs) were synthesized from the alkali fluorides and SnF 2 in methanol through a solvothermal route. Their 119 Sn Mössbauer spectra manifest divalent tin. The isomer shifts range from 3.09 to 2.94 mm s -1 . The pronounced lone-pair character at the Sn(II) centres is expressed by strong electric quadrupole splitting (1.91-1.95 mm s -1 ). The two, respectively four crystallographically independent tin sites in NaSnF 3 , KSnF 3 and RbSnF 3 could not be resolved in the 119 Sn spectra.