Collagen fiber immobilized Zr(Ⅳ)(ZrCF) was applied in the treatment of high concentration arsenate and fluoride co-existing containing wastewater. Adsorption behavior of As(Ⅴ) and F by ZrCF in co-existing containing wastewater was investigated. Taking the high concentration arsenate and fluoride co-existing containing wastewater from fertilizer plant as example, the effects of adsorbent dose, initial pH and contact time on adsorption performance were studied and the column experiment was carried out. Results suggested ZrCF had stronger appetency to As(Ⅴ) than to F. When the adsorbent dose was above 0.8 g, the concentration of arsenate and fluoride in effluent satisfied the national discharge standard. pH6.0 was the optimal acidity value, and As(Ⅴ) and F content decreased to the limited value after 6 h. When the effluent volume was 4.68 L, the fixed bed was saturated to As(Ⅴ) and F , and ZrCF could remove arsenate and fluoride simultaneously and efficiently.