In this work, a novel thin film based on porous polyethersulfone (PES) was designed and prepared applying polyvinyl alcohol (PVA) as a surface modifier and polyvinyl pyrrolidone (PVP) as a pore former. In this regard, after preparing the solution containing the appropriate amounts of PES, PVP, and PVA, the related membrane was prepared using phase inversion method. The characterization of the prepared porous PVA/PVP/PES membrane has been performed using attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), and EDX-mapping. The PVA/PVP/PES monolithic membrane was applied for thin film microextraction (TFME) of bisphenol A (BPA) in bottled water samples followed by spectrofluorimetry determination. The effect of PVA and PVP on the porosity and hydrophilicity of the prepared membrane and also on the extraction capability of the thin film was investigated. The fractional factorial design has been employed to screen essential factors affecting the extraction and desorption steps of TFME. Afterward, the significant factors were optimized applying the Box-Behnken design. The developed method’s limit of detection (LOD) was 0.3 ng mL−1 and its linear dynamic range (LDRs) was 1–1000 ng mL−1. The method repeatability (RSD %) based on intra-day precision, inter-day precision and inter-thin film repeatability with six replicate experiments in each item were 5.1, 8.9 and 9.5%, respectively, using spiked distilled water (100 ng mL−1). The applicability of the developed TFME-FL has been assayed by the determination of BPA in bottled mineral waters and the corresponded relative recoveries were in the range of 83.7 to 95.7 %.