This work introduces an environmental friendly sorptive composite for thin film microextraction (TFME). Chitosan as a biodegradable and biocompatible polymer was used to synthesis the thin film without use of any cross linker. Amino groups of chitosan can form hydrogen bonding with –OH functional groups of the analyte. For improvement the mechanical strength, chemical resistance and boosting adsorption capacity of the uniform composite, halloysite and montmorillonite were selected as suitable fillers. Adsorption efficiency of the two composites was compared for the TFME of 17?-ethinylestradiol in the same conditions. Results express halloysite composite is more efficient than ones. Other effective parameters such as amount of chitosan, filler percentage, ionic strength of aqueous solution, type and volume of desorption solvent, desorption condition and extraction time were investigated. Dynamic linear range of the method was 1.0-50.0 µg/L. Detection limit and precision were 0.4 µg/L and 9%, respectively. The method was also validated by the TFME of 17?-ethinylestradiol in tap water, river water and waste water by HPLC-FLD and recovery was found 67-106% for 2.0 and 10.0 µg/L.