In the title compound, [Li(2)(CF(3)SO(2)NSO(2)CF(3))(2)(CH(3)CN)(2)](n), two Li(+) cations reside on crystallographic inversion centers, each coordinated by six O atoms from bis(trifluoromethanesulfonyl)imide (TFSI(-)) anions. The third Li(+) cation on a general position is four-coordinated by two anion O atoms and two N atoms from acetonitrile mol-ecules in a tetra-hedral geometry.