BACKGROUND: The bioavailability of curcumin (Cur) is generally limited by its poor stability. However, it is beneficial to improve the stability of Cur by using self-assembled zein hydrolysate (ZH) as delivery carrier. This paper aimed to explore the formation mechanism of zein hydrolysate–curcumin nanocomplexes as a function of critical micelle concentration (CMC). RESULTS: In this work, The CMC of ZH (0.535 mg mL⁻¹) was obtained by the pyrene fluorescent probe method. ZH–Cur nanocomplexes undergo hydrogen bonding and hydrophobic interactions, and the fluorescence quenching effect was concentration dependent with the process of static quenching. Moreover, the differences of colloidal properties on ZH and ZH–Cur nanocomplexes were systematically compared by dynamic light scattering and scanning electron microscopy near CMC. ZH presented irregular spherical shapes and would aggregate to form micelles at the CMC and above. The tight micellar structure promoted more uniform size distribution (double peaks reduced) and higher potentials (over −30 mV) within 10 days. In addition, the nanocomplexes demonstrated an obvious core–shell structure. Within 10 days of storage, the particle size distributions were uniform and the potentials increased significantly, indicating that the micellar nanostructure made the Cur stably embedded in the hydrophobic core of ZH. Finally, ZH–Cur nanocomplexes effectively improved the water solubility and encapsulation rate (over 70%) of Cur. Moreover, over 90% of Cur was released steadily within 91 h. CONCLUSION: This work provided a theoretical basis for the application of amphiphilic peptide micellar nanostructure as novel food-grade nanocarriers to transport hydrophobic bioactive substances.