Ce 3+ doped solids find broad application, e.g. in phosphor converted light emitting diodes, utilizing the usually broad blue to yellow-orange emission of the respective phosphors. The red to infrared spectral range was not yet accessible with the activator Ce 3+ , even in nitride host materials. Here, we report on the nitridolithosilicates Li 38.7 RE 3.3 Ca 5.7 [Li 2 Si 30 N 59 ]O 2 F (RE = La, Ce, Y) with unique, red-shifted Ce 3+ luminescence. The materials were synthesized by solid-state metathesis reactions in tantalum ampules. The isotypic crystal structures exhibit a highly condensed threedimensional network made up of SiN 4 and LiN 4 tetrahedra. Crystal structures were refined from single-crystal and powder X-ray diffraction data. The results are supported by energy-dispersive Xray spectroscopy as well as charge distribution, lattice energy, and bond valence sum calculations. Optical band gaps of ≈4 eV were determined from diffuse reflectance UV/vis data using Tauc plots. The nitridolithosilicates are highly excitable from the UV to the green-yellow spectral range with a preferred excitation wavelength of λ exc ≈ 540 nm. The emission spectra peak is in the deep-red with λ em = 638−651 nm (fwhm ≈ 3600 cm −1 ). According to the unique absorption and emission properties, application as luminescent solar concentrators or in horticultural lighting appears promising.