Y₂O₃:Eu phosphor particles with a spherical shape, a fine size, and high brightness under vacuum ultraviolet (VUV) illumination were prepared by spray pyrolysis. The polymeric precursors were needed to modify the spray solution to prepare spherical particles. The use of only flux with the polymeric precursors did not produce dense and spherical Y₂O₃:Eu particles; that is, the produced particles were very porous. The addition of both a drying control chemical additive (DCCA) and boric acid to a spray solution containing polymeric precursors was found to produce Y₂O₃:Eu phosphor particles with a dense structure while maintaining the spherical morphology. According to X-ray diffraction (XRD) analysis, the DCCA induced an enhancement of crystallinity. The use of boric acid flux improved the photoluminescence (PL) intensity under VUV illumination. In addition, the use of both boric acid flux and a DCCA with polymeric precursors further improved the PL intensity owing to the enhancement of the morphology and the crystallinity.