Crystalline phosphors of Eu3+-doped titania (TiO2:Eu3+) were prepared by hydro and solvothermal synthesis with luminescent ion concentration of 2 mol.%. The structure and shape of the synthesized nanoparticles were characterized using X-ray powder diffraction, transmission electron microscopy, and Raman spectroscopy. Changes in the emission, excitation spectra, and the intensity decay of the photoluminescence for TiO2:Eu3+ nanoparticles were analyzed their phase composition. The photoluminescence of synthesized TiO2:Eu3+ crystalline phosphors depends on whether the said nanophosphors are formed from organometallic or inorganic precursors under hydro- and solvothermal conditions. Indeed, photoluminescence excitation at wavelengths ranging from 350–550 nm leads to splitting of electron dipole transitions into Stark components according to the symmetry of the Eu3+ surroundings. Also, both nanoparticles with the anatase structure and phosphors predominantly containing rutile showed very short photoluminescence lifetimes.