CeO₂ is an important rare earth (RE) oxide and has served as a typical oxygen storage material in practical applications. In the present study, the oxygen storage capacity (OSC) of CeO₂ was enhanced by doping with other rare earth ions (RE, RE = Yb, Y, Sm and La). A series of Undoped and RE–doped CeO₂ with different doping levels were synthesized using a solvothermal method following a subsequent calcination process, in which just Ce(NO₃)₃∙6H₂O, RE(NO₃)₃∙nH₂O, ethylene glycol and water were used as raw materials. Surprisingly, the Undoped CeO₂ was proved to be a porous material with a multilayered special morphology without any additional templates in this work. The lattice parameters of CeO₂ were refined by the least–squares method with highly pure NaCl as the internal standard for peak position calibrations, and the solubility limits of RE ions into CeO₂ were determined; the amounts of reducible–reoxidizable Ceⁿ⁺ ions were estimated by fitting the Ce 3d core–levels XPS spectra; the non–stoichiometric oxygen vacancy (V_O) defects of CeO₂ were analyzed qualitatively and quantitatively by O 1s XPS fitting and Raman scattering; and the OSC was quantified by the amount of H₂ consumption per gram of CeO₂ based on hydrogen temperature programmed reduction (H₂–TPR) measurements. The maximum [OSC] of CeO₂ appeared at 5 mol.% Yb–, 4 mol.% Y–, 4 mol.% Sm– and 7 mol.% La–doping with the values of 0.444, 0.387, 0.352 and 0.380 mmol H₂/g by an increase of 93.04, 68.26, 53.04 and 65.22%. Moreover, the dominant factor for promoting the OSC of RE–doped CeO₂ was analyzed.