To protect crops as well as human and animal health, the development of novel repellents based on biopolymers is critical for a growing world population. Here, novel aphid-repellent electrospun mats containing epoxidized ionic liquids (ILs) covalently bonded to the carboxyl or hydroxyl groups of poly-(lactic acid) (PLA) were designed to produce nonwoven mats. First, di-, tri-, and tetra-epoxidized imidazolium ILs were synthesized and incorporated in different weight fractions (3, 5, and 10 wt %) into the PLA solution. Then, the effect of ILs' microstructure, thermal properties, mechanical performance, and hydrophobic behavior were investigated. It was found that the incorporation of ILs resulted in a reduction of the fiber diameters while the mechanical properties of the mats, i.e., the three-dimensional fibrous porous structure, were maintained. Finally, the effect of these three ILs against the pea aphid Acyrthosiphon pisum (Harris) was evaluated for the first time, showing an attractive effect for the diepoxidized IL and a repellent effect for the tri- and tetra-epoxidized ILs. By exploiting the chemical nature of ILs, an environmentally friendly strategy can be developed to limit the need for chemical pesticides and petroleum-based polymers.