Zein, corn starch (CS), and orange-peel oil (OPO) extracted from orange peels were used to prepare novel corn starch/orange-peel oil/zein nanocapsules (OZN) bio-active food packaging materials. The results showed that the OZN were round, smooth and in compact morphology with an average diameter of 102.7 ± 10.5 nm from OPO and zein (3:10, ). By testing the turbidity and atomic force microscopy (AFM) of OZN and the mechanical properties and water vapor permeability of the composite films, the comprehensive properties of composite films with different mass ratios were analyzed. It showed that the addition of OZN improved the mechanical and moisture barrier properties and extended the release time of OPO. When the ratio of OZN and CS is 5:5, the highest elongation at break and tensile strengths is achieved, at values of 30.91% ± 2.52% and 12.19 ± 1.97 MPa respectively. The relative release concentration of OPO was highest at a ratio of 5/5, and over time it would last longer to maintain a higher release concentration. Besides, the oxidation resistance of the composite film was good, especially when the ration of starch CS to OZN was 5/5, it had the highest DPPH radical scavenging activity (30.16% ± 1.69%). Thus, it can be used as a bio-active edible food packaging film to ensure the safety of food products and reduce environmental pressure to some extent.