Removal of volatiles at 243 K from solutions of completely dissolved LnF3 (Ln=La–Dy and Y) and XeF2 (molar ratio 1 : 3) in anhydrous HF acidified with an excess of BF3 resulted in [Ln(XeF2)3](BF4)3 salts. Isolated solids are stable at 298 K and give similar Raman spectra. [La(XeF2)3](BF4)3 crystallizes in the monoclinic space group C2/m at 150 K. Each La atom is coordinated with three XeF2 ligands. Six F atoms provided by six bridging BF4 units, that connect the neighboring La3+ atoms into columns, complete the nine‐fold coordination of each La atom. Chemical reactions carried out in the same way but with molar ratio LnF3 : XeF2=1 : 1 yielded [Ln(XeF2)](BF4)3 salts (La ‐ Nd). Crystal structures of La and Nd salts are isotypic and crystallize in the monoclinic space group P21/m at 150 K (La) and 200 K (Nd). Each Ln center is coordinated by nine fluorine atoms provided by eight BF4 units and one XeF2 ligand. The BF4 groups interconnect the Ln atoms into two‐dimensional layers. With molar ratio LnF3 : XeF2=1 : 2 and the same synthetic approach, only La yielded [La(XeF2)2](BF4)3 salt. Prolonged pumping of [Ln(XeF2)n](BF4)3 (n=3, 2, 1) at 298 K or attempts of the isolation at 298 K resulted in products with lower content of XeF2 or in mixtures of various products. In addition to [Ln(XeF2)](BF4)3 and LnF3/BF3 products, the [Ln(XeF2)]F(BF4)2 salts (Ln=La, Nd, Sm, Eu, Tb, Dy and Y) also formed. The crystal structures of LaF(HF)(BF4)2 and LaF(BF4)2 side products were determined.