In this paper, the preparation technology of palygorskite-based compound material with palygorskite, starch, soluble glass was investigated, and the role of the compound material in the treatment of nitrophenol wastewater was studied. In addition, the effects of reaction time, addition amount of enzyme, H₂O₂ concentration and nitrophenol concentration on the removal of nitrophenol in wastewater by immobilized HRP was analyzed. The results showed that the optimal preparation conditions of palygorskite-based compound material were soluble glass 12%, starch 20%, calcination temperature 550℃ and calcination time 2 h. What is more important, the nitrophenol removal rate with immobilized HRP was higher than the original HRP. The optimal reaction conditions of removal of nitrophenol by immobilized HRP were reaction time 1.5 h, HRP 150 U, H₂O₂ concentration 0.12%, and nitrophenol concentration 100 mg/L. The nitrophenol removal rate was still above 60% when immobilized HRP was used for 7 times.