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Chromium is an important industrial raw material. As far as China is concerned, chromium is in great demand, which is dependent on imports and large emissions. So recovery of chromium has important economic and environmental protection value. The extraction and back extraction of Cr(III) from solution by the extractant diisooctyl phosphate (di‐2‐ethylhexylphosphoric acid [D2EHPA]) with n‐octanol as assistant and sulphonated kerosene as diluent was studied. The effects of saponification rate, phase ratio, temperature, condensation of extract, aging of extractant, and pH of aqueous phase on extraction equilibrium were discussed, and the formulation of extractant was optimized. The coordination number of the extraction reaction under specific conditions was discussed by the saturation capacity method. The extraction reaction kinetics were mathematically characterized by binary linear regression. The advantages and disadvantages of back extraction with H2SO4 or NaOH were compared. At last, a process to realize the recycling of extractant was obtained.