Barium fluoride (BaF₂) nanoparticles (NPs) with different sizes were produced through a hydrothermal microwave method (HTMW). The microstructural and electronic properties of the synthesized BaF₂ NPs were investigated using X-ray powder diffraction combined with the Rietveld refinement method and Williamson–Hall formalism, X-ray photoemission spectroscopy (XPS) and scanning electron microscopy (SEM). From the Rietveld method, we have found that the lattice parameter of BaF₂ NPs is smaller than that observed for BaF₂ in its crystal bulk form. These results demonstrated that the lattice parameter shows dependence on size of particle, increasing for larger particles, reducing strain-surface effects. XPS analyses showed that no other elements were present in the material. Photoluminescence (PL) studies in the vacuum ultraviolet (VUV) and visible (VIS) range were also performed to investigate the luminescence properties. The PL results showed a slight shift in the self-trapped exciton (STE) edge for samples with higher particle sizes. In addition, the band gap energy (E_g) was found to be around 10.5 eV for all samples. The observed lattice contraction/expansion was in concordance with the bond-order-length strength (BOLS) correlation mechanism. Therefore, we concluded that this behavior was purely due to surface stress as a result of particle size decreasing.