Edible films from chitosan (CH) containing various amount of acorn starch (AS) and eugenol (Eu) were developed by casting and solvent-evaporation method, and their physico-chemical, barrier, antimicrobial, antioxidant and structural properties were also investigated. The experimental data showed that an appropriate proportion of AS could improve the mechanical and barrier properties of the film, and the incorporation of Eu in the film significantly improved the flexibility, barrier, hydrophobicity, antimicrobial and antioxidant properties. The results showed that the optimum comprehensive properties of the film were obtained when the mass ratio of AS to CH was 0.9 and the content of Eu was 9%. Possible intermolecular interactions between CH, AS and Eu were confirmed by Fourier-transform infrared spectroscopy (FTIR). SEM indicated that a good compatibility was present between CH and AS, and Eu was well emulsified and dispersed in the film matrix network. TG and DTG curves further confirmed Eu present in the film matrix network. Such edible films can provide new ways for packaging industries in developing active packaging materials.