To effectively remove the dyes from wastewater, novel carboxymethyl cellulose/chitosan-CuO giant vesicles with dual function of adsorption and catalytic degradation were prepared. The vesicles were facilely obtained via blending chitosan solution and carboxymethyl cellulose/CuO mixed solution with sequent fast and slow stirring. The removal ratios of methyl orange (MO) and acid black-172 (AB) can reach 86.3% and 88.6% with the catalytic oxidation system of ammonium persulfate and vesicles. Compared with the CuO catalysis without the vesicles, the degradation rates of MO and AB increased by 1.3 and 3.1 times, respectively. The enhanced dye removal is ascribed to the excellent dye adsorption capacity of giant vesicles. Furthermore, the giant vesicles worked well in wide ranges of environmental pH and temperature, and exhibited excellent stability and reusability. This study provides a facile method to load catalyst onto polymeric giant vesicle with outstanding performance for the adsorption and catalytic degradation of dyes.