B‐complex vitamins are important compounds for the human body, namely for brain and cell function and preventing infections and diseases. However, the instability associated to these vitamins is a critical problem. Their encapsulation into delivery systems that are able to protect them against undesirable conditions can be one solution. The present study focuses on the encapsulation of the B‐complex vitamin at different concentrations (1, 5 and 10% w/w) by an electrohydrodynamic technique. The synergistic effect of the vitamins B in the enhancing antioxidant activity of the microstructures is investigated. Zein, a prolamine protein found in corn, was the chosen wall material. The matrices were analysed in terms of the surface morphology, encapsulation efficiency, antioxidant activity and release of the B‐vitamins from the zein microstructures. Spherical microbeads were produced with size between 0.32 and 0.38 μm and with high efficiency of encapsulation. Vitamins release profiles were obtained and the results suggested similar release profiles (in the range of 10 ‐ 40 hours) for the vitamin B3, vitamin B6, B3 plus B6 and B3 plus B6 plus B9. The Weibull model was used to adjust the experimental release profiles. Regarding the assessed antioxidant activity, it was possible to visualize an activity enhancement of the vitamin B3, vitamin B9, combined vitamins B6 and B9. Overall, the proposed encapsulation microsystems are a suitable alternative for the encapsulation of sensitive bioactive ingredients, such as vitamins, against external conditions, maintaining the indispensable stability essential for food, nutraceutical and pharmaceutical products.This article is protected by copyright. All rights reserved.