New materials based on self-assembled polyelectrolyte multilayers (PEM) thin film sorbents have been successfully developed. Several important coating parameters include the pH of the coating solution, the addition of salt to the coating solution, the dipping time, and the number of bilayers were optimized for drug extractors using the thin film micro extraction (TFME) technique. Optimum conditions were evaluated by the highest extraction performance for tricyclic antidepressant drugs (TCAs). Cellulose acetate membrane was chosen as the support material. Meanwhile, polyelectrolyte materials, namely poly (allyl amine hydrochloride) (PAAH) and poly(styrene sulfonic acid) (PSS) were chosen as coating materials. PAAH and PSS are deposited on the surface of the supporting material repeatedly. The results showed that the optimum coating conditions were pH PAAH 2 and PSS 2, no salt was added to the coating solution, the immersion time for each layer was 5 minutes, and the number of bilayers was 5. The optimized material was characterized by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), field emission-scanning electron microscopy (FESEM), and thermogravimetric-differential thermal analyzer (TG-DTA). The addition of PEM to the CA membrane also increased the thermal stability of CA-PEM. The results are inspiring and indicate that this sorbent has a great potential for thin film extraction sorbent and also suitable for thermal desorption application.