The invention relates to a technological method for extracting and separating quadrivalent cerium, thorium, and less-cerium trivalent rare-earth from rare earth sulfate solution. The rare earth sulfate solution, which is obtained through processing the rare-earth ores and contains the thorium and high-valence cerium, is used as raw material; synergistic extraction agent basing on P507 and P204 is adopted for extracting and separating; the cerium (4) and the thorium are extracted into an organic phase, then selective washing and back extraction are performed step by step to obtain the products including pure cerium and pure thorium, the trivalent rare-earth is left in a water phase, and then unsaponifiable P507 or the synergistic extraction agent basing on P507 is adopted to perform multistage fractional extraction to separate single rare earth elements after impurity removal. The technological methodn has the characteristics that the synergistic extraction agent basing on P507 and P204 is adopted, the thorium is easy to perform the back extraction, and extraction capacity is large, and the emulsification is not generated during the extraction process; the cerium (4), the thorium and trivalent rare-earth are extracted and separated in the same extraction system; both extraction and the separation adopt unsaponifiable extraction agent, and ammonia-nitrogen wastewater is not generated; in addition, the thorium is recovered as products, and the pollutions caused by thorium-containing waste residue and the ammonia-nitrogen containing wastewater are eliminated from headstream. Therefore, the technological method has the advantages of simple procedures, green environmental protection, and low manufacturing cost.