Oxyfluoride glass-ceramics (OxGCs) with the molar composition 80SiO2-20(1.5Eu3+: NaGdF4) were prepared with sol-gel following the “pre-crystallised nanoparticles route” with promising optical results. The preparation of 1.5 mol % Eu3+-doped NaGdF4 nanoparticles, named 1.5Eu3+: NaGdF4, was optimised and characterised using XRD, FTIR and HRTEM. The structural characterisation of 80SiO2-20(1.5Eu3+: NaGdF4) OxGCs prepared from these nanoparticles’ suspension was performed by XRD and FTIR revealing the presence of hexagonal and orthorhombic NaGdF4 crystalline phases. The optical properties of both nanoparticles’ phases and the related OxGCs were studied by measuring the emission and excitation spectra together with the lifetimes of the 5D0 state. The emission spectra obtained by exciting the Eu3+-O2− charge transfer band showed similar features in both cases corresponding the higher emission intensity to the 5D0→7F2 transition that indicates a non-centrosymmetric site for Eu3+ ions. Moreover, time-resolved fluorescence line-narrowed emission spectra were performed at a low temperature in OxGCs to obtain information about the site symmetry of Eu3+ in this matrix. The results show that this processing method is promising for preparing transparent OxGCs coatings for photonic applications.