Acetylspiramycin pharmaceutical wastewater is a kind of biorefractory organic wastewater. It is meaningful academically and actually that the Photo-Fenton method is used in the oxidation and degradation of the effluent water. After pretreatment of the wastewater with COD 6169mg/L, the oxidation reactions were proceeded which the oxidation effects were evaluated by the changes of COD and BOD5. Orthogonal experiment was applied based on the single factor experiment, the optimal process conditions were determined as follows, the volume ratio of H2O¬2: FeSO4•7H2O 1:1, the dosage of FeSO4•7H2O 7.8mmol/L, the pH value 3.0 and on the solar ray radiation respectively. Under the said conditions, the ratio of BOD5/COD went from 0.15 to 0.24 indicating that biodegradability had improved. Meanwhile COD reduced largely. The removal rate of COD calculated on this stage reached 78.9%. Added to the former pretreatment process, the total removal rate of COD was up to 88.6%. It was higher than other disposal technologies of antibiotic pharmaceutical wastewater and displayed a promising future.