Structural modification of Cotton (Cot) fiber was carried out using ε-caprolactone (CL) as a monomer and oxydianiline (ODA) as a Schiff base forming agent in the presence of VO catalyst in dimethylsulfoxide medium for 24h under air atmosphere (0.10MPa) at 80°C. The obtained products were analyzed for the characteristics and also for its adsorption of hexavalent chromium (Cr(VI)) and rhodamine 6G (R6G) dye molecules. The H NMR spectrum confirms the Schiff base formation at 8.7ppm. The adsorption study confirms the Pseudo second order kinetics with Langmuir adsorption model. The structurally modified Cot fiber based Schiff base exhibited the highest adsorption behavior through chemical interaction forces. The thermodynamic parameters were determined and confirmed the endothermic adsorption process.