Α novel, green, and facile fabric phase sorptive extraction (FPSE) prior to high pressure liquid chromatography with diode array detection (HPLC-DAD) methodology was developed for the efficient extraction and quantitative determination of tocopherols (α-, sum of (β+γ), and δ-) in edible oils. Among several highly hydrophobic FPSE membranes, sol-gel polycaprolactone-polydimethylsiloxane-polycaprolactone (sol-gel PCAP-PDMS-PCAP) coated polyester FPSE membrane was found as the most efficient in extracting tocopherol homologues from edible oil samples. To maximize the extraction efficiency of FPSE membrane, major parameters of FPSE including the membrane size, sample loading time, the choice of the appropriate elution solvent and the elution solvent volume, desorption time, and the influence of stirring were systematically optimized. The developed FPSE-HPLC-DAD methodology was validated and presented adequately low limits of detection (LODs) and limits of quantification (LOQs) over the ranges 0.05–0.10 μg/g, and 0.17–0.33 μg/g, respectively. The RSD% of the within-day and between-day assays were lower than 1.3, and 11.8, respectively, demonstrating good method precision. The trueness of the method was assessed by means of relative percentage of recovery and ranged between 90.8 and 95.1% for within-day assay, and between 88.7–92.8% for between-day assay. The developed methodology was applied in the analysis of edible oils.