A new lanthanide silicate system, Na K[Ln Si O ] (Ln=Lu, Yb/ Er, Lu/Eu, or Lu/Yb/Er), comprising microcrystals embedded in an amorphous siliceous matrix, obtained by sintering at 1373 K a Na K[Ln Si O ]⋅3 H O nano-crystalline precursor, is reported. The crystal structure of these lanthanide silicates was solved from high-resolution synchrotron power X-ray diffraction data collected at 110 K, and further supported by Si MAS NMR and Eu luminescence. The materials crystallize in the Pī triclinic centrosymmetric space group, exhibiting a dense framework consisting of hexameric [Si O ] cyclosilicate units, and chains of two distinct {LnO } octahedra. Na K[(Lu Yb Er ) Si O ] is the first example of a lanthanide silicate operative as a near-infrared ratiometric luminescent thermometer, with good sensitivity at cryogenic temperatures (<100 K). Upon excitation at 903 nm, the ratio between the F → F (Yb ) and I → I (Er ) emissions was used for sensing temperature in the 12-450 K range, reaching a maximum thermal sensitivity of 2.6 % K at 26.8 K.