The main objectives of this work are to prepare the chitosan(CH)/PVA biomaterials for the selective separation of 4-isopropylphenol (4IPP) as a phenolic. In order to improve the selective separation, CH/PVA biomaterials was also synthesized using benzoic acid (BA) or p-toluic acid (pTA) which have a similar structure with 4IPP as the target material. The CH/PVA biomaterials were prepared by casting method and UV irradiation process. Physical properties such as tensile strength (TS), elongation at break (%E), swelling behavior (SB), and solubility (S) for prepared biomaterials were investigated. The adsorption properties were evaluated by the adsorption kinetics, binding isotherm, Scatchard plot analysis, adsorption of materials with structures similar to target molecules, and selectivity factor (α). The results of the evaluation indicate that the prepared CH/PVA biomaterials have high separation abilities and selectivity.