Zein is the major storage protein from corn with strong hydrophobicity and unique solubility and has been considered as a versatile food biopolymer. Due to the special tertiary structures, zein can self-assemble to form micro- and nano-particles through liquid–liquid dispersion or solvent evaporation approaches. Zein-based delivery systems have been particularly investigated for hydrophobic drugs and nutrients. Recently, increasing attention has been drawn to fabricate zein-based advanced drug delivery systems for various applications. In this review, the molecular models of zein tertiary structure and possible mechanisms involved in zein self-assembly micro- and nano-particles are briefly introduced. Then, a state-of-the-art introduction and discussion are given in terms of preparation, characterization, and application of zein-based particles as delivery systems in the fields of food science, pharmaceutics, and biomedicine. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40696.