Abstract The encapsulation of the light sensitive model β-carotene, a colorant and antioxidant molecule widely used in the food industry, has been successfully achieved in ultrafine fibers of zein prolamine, a sustainable agropolymer, by means of electrospinning. Fiber capsules were in the micro- and nanorange in the cross-section and the encapsulation preserved the fluorescence of the polyene molecules. Observations with confocal Raman imaging spectroscopy showed that the antioxidant was stable and widely dispersed inside the zein fibers but agglomerated in some areas. Nevertheless, a significant increase in the light stability of the β-carotene when exposed to UV–vis irradiation was determined for the encapsulated compound. As a result, electrospinning of zein prolamine shows an excellent outlook for its application in the stabilization of light sensitive added-value food components.