The effects of common precursors used in the synthesis of CeO2 nanopowders were investigated, and the structural and spectral properties of the resulting products were compared. Two cerium (III) salts, i.e., Ce(NO3)3·6H2O and CeCl3·7H2O, and two cerium (IV) salts, i.e., Ce(SO4)2·4H2O and (NH4)2Ce(NO3)6 were applied. The proposed procedures for the CeO2 preparations were realized using the same hydrothermal treatment conditions. The products were characterized using X-ray powder diffraction (XRD) and thermogravimetric (TG) analysis, and the morphology was determined using scanning (SEM) and transmission electron microscopy (TEM). The spectral properties of the obtained nanopowders were characterized by FT-IR, Raman scattering and UV–vis spectroscopy. The results revealed the influence of the precursors on the crystallinity, crystallite size, band gap energy, morphology and purity of the synthesized samples.