To develop biodegradable, sustainable, and environment-friendly functional food-packaging materials, gelatin/zein/glucose nanofibers were fabricated through air-assisted electrospinning and then crosslinked by the Maillard reaction under mild conditions (60 °C and 50% relative humidity) in this study. Compared to traditional electrospinning, air-assisted electrospinning increased the yield of nanofibers by 10 times, and the average diameter from 263 nm to 664 nm, while the airflow facilitated uniform and smooth nanofiber formation. During the Maillard reaction in 0-5 days, the gelatin/zein/glucose showed no morphology change. Fourier transform infrared spectra analysis indicated that gelatin interacted with zein through hydrogen bonding and the occurrence of the Maillard reaction among the protein and glucose molecules. After four days of Maillard reaction, the nanofibers presented higher thermal stability, the most hydrophobic surface (water contact angle: 133.6°), and stiffer network structure (elastic modulus of 38.63 MPa, tensile strength of 0.85 MPa). Overall, Maillard-reaction-crosslinked gelatin/zein/glucose nanofibers showed favorable physical properties, which suggests their potential for application in food-active packaging.