Pear psyllids are the main vectors of the pathogen ‘Candidatus Phytoplasma pyri’ causing pear decline. Based on earlier reports, we tested the behavioral activity of the major synthetic compounds of clove essential oil (eugenol, eugenyl acetate, and β-caryophyllene) against Cacopsylla pyri and C. pyricola. Of six mixtures tested in olfactometer assays, a formulation consisting of three specific compounds (M6 mixture) demonstrated a repellent effect on both psyllid species. In addition, this formulation masked the odor of the host Pyrus communis cv. Williams Christ, disturbing the host finding ability of C. pyri. Electrospun fibers were produced with biocompatible polymers poly(ε-caprolactone), cellulose acetate, and solvents formic acid and acetic acid, loaded with the repellent mixture to test their efficacy as dispensers of repellents in laboratory and field. The fibers produced were repellent to C. pyri and effectively masked the odors of pear plants in olfactometer tests. In a pear orchard, we compared the captures of pear psyllids in green-colored attractive traps treated with nanofibers loaded with M6 mixture or unloaded nanofibers (blank). The result showed no differences in the captures of C. pyri between treatments. The release rates of volatiles from the fibers were evaluated weekly over 56 days. The fibers were able to entrap the major compound of the M6 mixture, eugenol, but the release rates were significantly reduced after 21 days. Our results suggest that biodegradable dispensers could be produced with electrospinning, but further improvements are necessary to use repellents as a management tool for pear psyllids in the field.