The influence of the addition of 1 mol% Tm₂O₃ on the nanocrystallization of LaF₃ in a glass of composition 55SiO₂–20Al₂O₃–15Na₂O–10LaF₃ (mol%) has been studied. Tm₂O₃ affects the phase separation in the glass and delays the onset of crystallization with respect to the undoped glass. Additionally, the maximum LaF₃ crystal size is slightly greater than that in the undoped glass–ceramics. The microstructural and compositional changes in the glass matrix have been studied using several techniques, including viscosity, dilatometry, X-ray and neutron diffraction (XRD, ND), quantitative Rietveld refinement, transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and Raman spectroscopy. Photoluminescence measurements indicate that the Tm³⁺ ions are distributed between the glassy matrix and LaF₃ crystals. Eu₂O₃ has been used as structure probe and part of the Eu³⁺ ions are reduced to Eu²⁺ when incorporated in the LaF₃ nano-crystals. Up-conversion spectra under IR-excitation show a higher intensity of the blue emission in the Tm-doped glass–ceramic compared with that in the glass.