It is known that the initiation of photodynamic therapy (PDT) in deep-seated tumors requires the use of X-rays to activate the reactive oxygen species generation in deep tissues. The aim of this paper is to synthesize X-ray nanophosphors and analyze their structural and luminescence characteristics to push the PDT process deep into the body. The article deals with BaGdF5:Eu3+, BaGdF5:Sm3+, and BaGdF5:Tb3+ nanophosphors synthesized using microwave synthesis. It is found that the nanoparticles are biocompatible and have sizes 5–17 nm. However, according to the analysis of X-ray excited optical luminescence, BaGdF5:Sm3+ nanophosphors will not be effective for treating deep-seated tumors. Thus, BaGdF5:Eu3+ and BaGdF5:Tb3+ nanoparticles meet the requirements for the subsequent production of nanocomposites based on them that can be used in X-ray photodynamic therapy.