Based on biosorption and photodegradation coupling technology, a novel adsorbent, which not only adsorbs the heavy metal ions but also degrades organic compound, was prepared by immobilization of nano-TiO2 on chitosan matrix. Degradation characteristic of Rhodamine B (Rh.B) was investigated by TiO2-chitosan adsorbents. The results showed that degradation ratio reached 94.3% by 0.2 g adsorbents under ultraviolet radiation light (UV) at initial Rh.B concentration of 10 mg/L and optimal pH of 9.0. Degradation and adsorption behavior characteristics were discussed in the presence of binary pollutants (Rh.B and Ag+). The coexistence of Ag+ intensely inhibited the degradation ability of Rh.B. Higher Ag+ concentration weakened the degradation ability. However, Rh.B did not affect the adsorption capacity of Ag+. Moreover, TiO2-chitosan adsorbent contributed to a higher degradation ability of organic pollutants in practical wastewater. Degradation capacity of contaminants in paper-making wastewater reached 60.8 mg/g at the initial COD concentration of 2,000 mg/L.