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Abstract Progesterone (P4), commonly administered in high doses for endometrial cancer palliative management, has limitations in current delivery systems. This preliminary in vitro drug release study introduces electrospun patches to offer a new perspective on P4 delivery. The study aimed to assess the influence of the surfactant polysorbate 80 (PS80) on the release of P4 from polycaprolactone (PCL) fibers. The PS80 effects are examined to inform the fine‐tuning of the fibre generation process. Patches developed, PCL wet (with PS80) and PCL dry (without PS80), showed encapsulation efficiencies of 76% and 42%, respectively. The dose levels studied are 6.1 mg for PCL wet and 4.4 mg for PCL dry samples. Molecular studies show that higher surfactant levels improved P4‐polymer mixing, enhancing dissolution and release rates. Patches with PS80 released 66% of the drug in 17 h, while those without released only 51%. Release data best fit the Weibull model, showcasing promise for these patches in transdermal P4 delivery. This study offers a non‐invasive option compared to traditional methods and underscores the need for further research to confirm the patches' clinical effectiveness for potential use in gynecological oncology.