A monodisperse spherical Y2O3:Eu3+ phosphor was prepared by a homogeneous precipitation method. The mean size of the phosphor particles (MSPP) was successfully controlled by changing the volume ratio of normal alcohol (RA) (propanol) in the solvents mixed between deionized water and normal propanol. When the RA was increased from 0 to 0.7, the MSPP decreased while maintaining a high yield of >95%. Although the prepared phosphor samples were fired at the same temperature, the thermal energy was delivered more efficiently into the inner side of the phosphor particles with the decrease of the MSPP. Therefore, the crystallinity and also the photoluminescence (PL) intensity of the phosphor increased with the decrease in the MSPP. In addition, because the numbers of Eu3+ ions located near the particle surfaces increased with the decrease of particle size, the ratio of PL intensity caused by the 5D0–7F2 transition to that caused by 5D0–7F1 transition increased from 10.8 to 12.7 with the decrease in MSPP.