Zein electrospun nanofibers have poor water resistance, which restricts its applications in food preservation. To improve the water resistance of nanofibers, zein/ethyl cellulose (EC) hybrid nanofibers were prepared at different ratios. Besides, we also encapsulated cinnamon essential oil (CEO) into electrospun fibers for Agaricus bisporus preservation. As the weight ratio of EC increased from 0% (ZE-10) to 100% (ZE-01), the viscosity of electrospinning solutions gradually increased from 80.33 ± 19.23 mPa·s to 756.78 ± 22.48 mPa·s, resulting in sufficient chain entanglement for the preparation of uniform fibers. The average diameters of ZE-01, ZE-12, ZE-11, ZE-21, and ZE-10 nanofibers were 326 ± 53 nm, 267 ± 31 nm, 237 ± 51 nm, 292 ± 45 nm, and 362 ± 70 nm, respectively. The hydrogen bonds between the hydroxyl groups of ethyl cellulose and the amino groups of zein decreased the amount of free hydrophilic group, thus improving water resistance of nanofibers. Food packaging potential was evaluated using Agaricus bisporus. The zein/EC nanofibers loaded CEO significantly decreased weight loss and maintained the firmness of the Agaricus bisporus, and improved the quality of the Agaricus bisporus during storage.