²⁷Al and ²³Na NMR satellite transition spectroscopy and 3Q magic-angle-spinning spectra are recorded for three compounds from the ternary NaF−CaF₂−AlF₃ system. The quadrupolar frequency ν_Q, asymmetry parameter η_Q, and isotropic chemical shift δ_iso are extracted from the spectrum reconstructions for five aluminum and four sodium sites. The quadrupolar parameters are calculated using the LAPW-based ab initio code WIEN2k. It is necessary to perform a structure optimization of all compounds to ensure a fine agreement between experimental and calculated parameters. By a comparison of experimental and calculated values, an attribution of all of the ²⁷Al and ²³Na NMR lines to the crystallographic sites is achieved. High-speed ¹⁹F NMR MAS spectra are recorded and reconstructed for the same compounds, leading to the determination of 18 isotropic chemical shifts. The superposition model developed by Bureau et al. is used, allowing a bijective assignment of the ¹⁹F NMR lines to the crystallographic sites.