The beta-modification of Li3CrF6 was prepared by heating an appropriate mixture of LiF and CrF3 at 820 degrees C in an argon-filled quartz glass ampoule with subsequent slow cooling to room temperature. beta-Li3CrF6 is isotypic to beta-Li3VF6 and crystallizes in space group C2/c with a = 14.381(1), b = 8.605(1), c = 10.012(1) Angstrom, beta = 94.85(1)degrees. The structural parameters were refined using single crystal data. A comparison of its structure with that of other beta-Li3MF6 (M = Ti, Ga, and Al) compounds is made for the analysis of a static Jahn-Teller effect within quasi-isolated [TiF6](3-) octahedra. Emphasis is given to the geometry and coordination number of various LiFn polyhedra. The magnetic moment of the title compound was close to that of a free-ion value. Calculations of the Madelung part of the lattice energy (MAPLE) were performed to ascertain the accuracy of the positional parameters of various atoms in the structure.