Zinc oxide doped with europium has been prepared by high temperature calcination method using ZnO, Eu2O3, and LiOH. Structural characterization by X-ray diffraction and optical studies by photoluminescence spectroscopy together give evidence that Eu3+ is going to the substitutional site of Zn2+. The concentration of chemicals used, sintering temperature, and time are optimized with photoluminescence excitation spectroscopy for a sharp and intense red signal which is a signature of Eu3+. Characteristic red emission at 607 nm is observed using high-energy excitation along with the native deep center emission of ZnO peaking around 525 nm.