Novel fluorophosphate glass systems with the chemical composition of 20NaF–60P2O5–20Na2O doped with 3 wt % of different transition metals (CuO, CoO, Fe2O3, and NiO) were fabricated by conventional melting. The influence of transition metals doping on the photoluminescence (PL) and dielectric properties of base systems is investigated. The sample doped with Fe2O3 displayed the lowest PL intensity compared to the highest PL intensity for CuO. Adding CuO and Fe2O3 to the base composite enhances the dielectric parameters slightly. The highest energy density values are observed for the base composite doped with CuO, and Fe2O3, while the lowest energy density values are detected for NiO and CoO-doped systems. The improved ac conductivity of the base system upon adding CuO and Fe2O3 is ascribed to increasing the polaron hopping between their ions in the valence states. However, adding CoO and NiO to the base composite may hinder the charge carriers’ motion and decrease its conductivity. The non-Debye-type is the dominant relaxation process for all the systems under investigation.