The isotypic layered oxonitridosilicates Li(14)Ln(5)[Si11N19O5]O2F2 (Ln = Ce, Nd) have been synthesized using Li as fluxing agent and crystallize in the orthorhombic space group Pmmn (Z = 2, Li14Ce5[Si11N19O5]O2F2: a = 17.178(3), b = 7.6500(15), c = 10.116(2) angstrom, R1 = 0.0409, wR2 = 0.0896; Li14Nd5[Si11N19O5]O2F2: a = 17.126(2), b = 7.6155(15), c = 10.123(2) angstrom, R1 = 0.0419, wR2 = 0.0929). The silicate layers consist of dreier and sechser rings interconnected via common corners, yielding an unprecedented silicate substructure. A topostructural analysis indicates possible ID ion migration pathways between five crystallographic independent Li positions. The specific Li-ionic conductivity and its temperature dependence were determined by impedance spectroscopy as well as DC polarization/depolarization measurements. The ionic conductivity is on the order of 5 X 10(-5) S/cm at 300 degrees C, while the activation energy is 0.69 eV. Further adjustments of the defect chemistry (e.g., through doping) can make these compounds interesting candidates for novel oxonitridosilicate based ion conductors.