Electrospun ultra‐fine poly(vinyl alcohol)/permutite fibrous film loaded with cinnamaldehyde essential oil was successfully fabricated.The morphology of fibrous filmswas characterized by scanning electron microscopy (SEM) and atomic force microscope (AFM). The fibrous film exhibited microstructure features with high porosity with the pore size distributed ranging from 1.7 nm to 56.7 nm. And the root‐mean‐squared roughness of fibers lifted to 546.5 nm when the addition of cinnamaldehyde essential oil (CEO) reached 0.25 mL. Attenuated total reflectance‐fourier transform infrared (ATR‐FTIR) spectroscopyconfirmed the existence of CEO in fibrous films and revealed physical interaction rather than chemical interactions existing between the film matrix and CEO. Endothermic peaks presented in differential scanning calorimetry (DSC) profile were probably rooted from existed mesoporous adsorption between the highly porous film matrix and CEO. Furthermore, the PVA/permutite/CEO fibrous film prolonged the shelf life of strawberries, confirming that the PVA/permutite/CEO fibrous film may be of interest for the development of active food packaging. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46117.