Because of its sensitivity to the atomic scale environment, solid-state NMR offers new perspectives in terms of structural characterization, especially when applied jointly with first-principles calculations. Particularly, challenging is the study of actinide-based materials because of the electronic complexity of the actinide cations and to the hazards due to their radioactivity. Consequently, very few studies have been published in this subfield. In the present paper, we report a joint experimental theoretical analysis of thorium tetrafluoride, ThF4, containing a closed-shell actinide (5f(0)) cation. Its crystalline structure has been revisited in the present work using powder neutron diffraction experiments. The F-19 NMR parameters of the seven F crystallographic sites have been modeled using an empirical superposition model, periodic first-principles calculations, and a cluster-based all-electron approach. On the basis of the atomic position optimized structure, a complete and unambiguous assignment of the F-19 NMR resonances to the F sites has been obtained.