XeF+MF6- (M = As, Sb) reacts with (C6F5)2S in HF to form (C6F5)2SF+MF6-. The deeply violet sulfonium salts can be kept without decomposition up to 24 h at room temperature. The hexafluoroantimonate salt crystallizes in the monoclinic space group P2(1)/n with a = 1056.4(7) pm, b = 1446.3(10) pm, c = 1102.9(8) pm, beta = 91.29(6)-degrees und Z = 4. The SF-bond distance with 158.4(3) pm is of unusual length. Cations and anions are connected via interionic fluorine contacts to an infinite chain, in which cations and anions form to ABAB sequence along the chain.