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In this study, tannic acid (TA), a natural antioxidant, is successfully encapsulated into a plant‐based guar gum fibrous mat by electrospinning without using an organic solvent. An upper threshold of 10 wt% TA (based on the dry weight of guar gum [GG]) and 2 wt% guar gum is the optimum composition to achieve a defect‐free structure through electrospinning. The obtained nanofibers have a mean diameter of 96 ± 22 nm. The effect of the encapsulated TA in the fibrous mat (200 ppm) on the oxidation of unrefined flaxseed oil (FO) is investigated over 30 days of storage at an elevated temperature (60 °C) and compared with the effect of butylated hydroxytoluene (BHT), a synthetic antioxidant, and non‐encapsulated TA at the same concentrations. Changes in the fatty acid composition, the conjugated diene content, the peroxide value, the content of thiobarbituric acid reactive substances (TBARS) and the p‐anisidine content are monitored as indicators of the oxidative stability. The TA fibrous mat exhibits different inhibitory effects on the oxidation of unsaturated fatty acids and is more effective than non‐encapsulated TA and BHT in reducing the rate of primary oxidation and secondary oxidation of FO as evaluated by all the oxidation indicators except the TBARS values for which BHT displays the greatest inhibition. Overall, the results demonstrate that the encapsulation of natural antioxidants into fibrous mats could potentially be used to preserve edible oils. Practical Applications: This is the first paper using plant‐based fibrous mats encapsulating natural antioxidant to improve the oxidative of flaxseed oil (FO) during storage. Compared with macro Tannic acid (TA), encapsulating TA in nano‐scale delivery system is more effective in delaying both the primary and secondary oxidation reactions of FO throughout the entire storage time. The results demonstrate that encapsulation of TA in fibrous mat could be potentially used to preserve oil. The formation of this nanofiber mat in this system is manufactured without using any synthetic chemicals. The plant‐derived components (GG and TA) are both recognized as safe by FDA and even edible. It can be directly added to crude oil systems during oilseed refining processing or used as coating material to fix on the surface of existing packaging bottle in order to prevent edible oil from oxidation, which would be beneficial in oil preservation and other related fields. This is the first paper using plant‐based nanoscale delivery system encapsulating natural antioxidant to improve the oxidative of flaxseed oil during storage. The plant‐derived components (guar gum and tannic acid) are both recognized as safe by FDA and even edible. The simple preparation process, effectiveness, and food‐grade functionality provide a novel alternative to synthetic antioxidants to protect edible oil from oxidation. [ABSTRACT FROM AUTHOR]