White powder samples of the new complex fluorides Tl2SnF6 and Tl2TiF6 have been prepared by heating appropriate mixtures of TlF and SnF4 or TiF4 at 300 degrees C in a Pt ampoule under an argon atmosphere. Tl2SnF6 and Tl2TiF6 are isotypic to K2GeF6 and crystallize in P (3) over bar m1, with a = 609.0(1), c = 487.8(1) pm for Tl2SnF6 and a = 596.1(1), c = 485.6(1) pm for Tl2TiF6. The structural parameters have been refined by Rietveld analysis from powder data. Calculations of the Madelung part of the lattice energy (MAPLE) and band structure calculations were performed, to discuss the chemical bonding and the stereochemical activity of the lone pair at Tl+.