ABSTRACT Active biodegradable poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) melt mixed nanocomposites and bilayer structures containing copper oxide (CuO) nanoparticles were developed and characterized. The bilayer structures consisted of a bottom layer of compression molded PHBV3 (3% mol valerate) coated with an active electrospun fibers mat made with CuO nanoparticles and PHBV18 (18% valerate) derived from microbial mixed cultures and cheese whey. The results showed that the water vapor permeability increased with the CuO addition while the oxygen barrier properties were slightly enhanced by the addition of 0.05 wt % CuO nanoparticles to nanocomposite films but a negligible effect was registered for the bilayer structures. However, the mechanical properties were modified by the addition of CuO nanoparticles. Interestingly, by incorporating highly dispersed and distributed CuO nanoparticles in a coating by electrospinning, a lower metal oxide loading was required to exhibit significant bactericidal and virucidal performance against the food‐borne pathogens Salmonella enterica, Listeria monocytogenes, and murine norovirus. The biodisintegration tests of the samples under composting conditions showed that even the 0.05% CuO‐coated structures biodegraded within 35 days. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45673.