The research of active biodegradable multilayer materials are of current interest for developing functional and sustainable packages able to guarantee the microbiological safety of food. In this work, an active biodegradable trilayer packaging system composed of (1) an external layer of extruded polylactic acid (PLA) film, (2) an intermediate layer of electrospun PLA loaded with ethyl lauroyl arginate (LAE) and cellulose nanocrystals (CNC), and (3) an inner layer of chitosan processed by coating, was developed. Optical, structural, and thermal properties were evaluated. Furthermore, a mathematical mass transfer model focused on the fibers structure was developed to study the LAE release to aqueous and fatty food simulants. Compared to extruded PLA, the trilayer material was white and opaque with a Delta E = 2.6. Furthermore, the processing of material produced a scarce interaction between their components and its crystallinity was increased by 85%. K coefficients were lower than 100 evidencing the high affinity of LAE for both simulants, while D coefficients approximate to 0.5x10(-17)m(2)s(-1) demonstrated the slow diffusion of LAE through the material.