This study aimed to develop core-shell nanofibers by emulsion electrospinning using zein-stabilized emulsions to encapsulate camellia oil effectively. The increasing oil volume fraction (φ from 10% to 60%) increased the apparent viscosity and average droplet size of emulsions, resulting in the average diameter of electrospun fibers increasing from 124.5nm to 286.2nm. The oil droplets as the core were randomly distributed in fibers in the form of beads, and the core-shell structure of fibers was observed in TEM images. FTIR indicated that hydrogen bond interactions occurred between zein and camellia oil molecules. The increasing oil volume fraction enhanced the thermal stability, hydrophobicity, and water stability of electrospun nanofiber films. The core-shell nanofibers with 10%, 20%, 40%, and 60% camellia oil showed encapsulation efficiency of 78.53%, 80.25%, 84.52%, and 84.39%, respectively, and had good storage stability. These findings contribute to developing zein-based core-shell electrospun fibers to encapsulate bioactive substances.