Arachidonic acid (AA) is an n‐6 polyunsaturated 20‐carbon fatty acid taking important immunomodulatory roles in infant growth, brain development, and health. However, one of the major drawbacks of polyunsaturated fatty acids is their high susceptibility to oxidation followed by unpleasant odors. Microencapsulation has been proposed as an excellent strategy to solve these problems. In this work, coaxial electrospray was utilized to fabricate AA/zein microcapsules with core‐shell structures which were verified by scanning electron microscopy, transmission electron microscopy, and confocal laser scanning microscopy. Microcapsules morphology was conveniently controlled through electrospray parameters and AA was centralized in the core. The microcapsule diameter ranged from 1 to 7 μm. Results of peroxide values and GC–MS demonstrated that AA in microcapsules possess improved oxidative stability and the unpleasant odors of AA oil was inhibited. The results indicate coaxial electrospray is a useful and convenient tool to fabricate core‐shell microcapsules with immiscible materials, which will broaden the potential use of microcapsules as nutrition fortifiers in the food industry.

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