Electrostatic spinning, as an effective method for the preparation of nanofibers, has the advantages of wide applicability, simple production equipment, mild operating conditions, and no pollution. The use of environmentally friendly natural polymer cellulose as the electrostatic spinning polymer can be used to realize the controlled release of antimicrobial agents, thus extending the shelf life of fruits and vegetables. Three kinds of nanofibers, T-PVA, T-CPVA and T-SCPVA, are prepared by us through the coaxial electrostatic spinning process. In this process, polyvinyl alcohol (PVA), nanofibers (CNF)-PVA (CPVA) and SiO2/CNF-PVA (SCPVA) are used as shell spinning solutions, and thyme essential oil (TEO) is used as core spinning solution. The slow-release characteristics and antibacterial effects of these nanofibers are systematically analyzed by us. The results show that the nanofibers prepared by coaxial electrostatic spinning have uniform diameter distribution and complete morphology, and the fiber diameters are distributed in the range of 70–110 nm. The release peaks of T-PVA, T-CPVA and T-SCPVA are reached on the 12th, 16th and 18th days, respectively, and the additions of CNF and SiO2 can effectively regulate the pore space on the surface of the fibers and control the release of TEO. In addition, T-PVA, T-CPVA and T-SCPVA nanofibers show good inhibitory effects on Aspergillus niger, Penicillium oryzae, Escherichia coli and Staphylococcus aureus.