A porous CeO2 was synthesized following the addition of guanidine carbonate to a Ce3+ aqueous solution, the subsequent addition of hydrogen peroxide and a final hydrothermal treatment. The optimal experimental parameters for the synthesis of porous CeO2, including the amounts of guanidine carbonate and hydrogen peroxide and the hydrothermal conditions, were determined by taking the adsorption efficiency of acid orange 7 (AO7) dye as the evaluation. A template−free hydrothermal strategy could avoid the use of soft or hard templates and the subsequent tedious procedures of eliminating templates, which aligned with the goals of energy conservation and emission reduction. Moreover, both the guanidine carbonate and hydrogen peroxide used in this work were accessible and eco−friendly raw materials. The porous CeO2 possessed rapid adsorption capacities for AO7 dye. When the initial concentration of AO7 was less than 130 mg/L, removal efficiencies greater than 90.0% were obtained, achieving a maximum value of 97.5% at [AO7] = 100 mg/L and [CeO2] = 2.0 g/L in the first 10 min of contact. Moreover, the adsorption–desorption equilibrium between the porous CeO2 adsorbent and the AO7 molecule was basically established within the first 30 min. The saturated adsorption amount of AO7 dye was 90.3 mg/g based on a Langmuir linear fitting of the experimental data. Moreover, the porous CeO2 could be recycled using a NaOH aqueous solution, and the adsorption efficiency of AO7 dye still remained above 92.5% after five cycles. This study provided an alternative porous adsorbent for the purification of dye wastewater, and a template−free hydrothermal strategy was developed to enable the design of CeO2−based catalysts or catalyst carriers.