Elaboration of electrospun nanofibrous poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBHV)-based mats was implemented through two routes to obtain antibacterial material containing carvacrol, a phenolic compound extracted from essential oils. The first strategy relied on a direct blend of PHBHV and carvacrol/-cyclodextrin inclusion complexes, PHBHV (carvCD-IC), while the second approach implied the elaboration of multilayered scaffold via the introduction of poly(β-CD-epichlorohydrin), PolyCD. The PolyCD/carv-based mat was electrospun between two hydrophobic PHBHV mats. Scanning Electron Microscopy analysis of mats showed uniform and beadless fibers. The three layered materials [PHBHV-(PolyCD/carv)-PHBHV] is sufficient to ensure optimal antiradical activity (RSA of 88.6%) and exhibit interesting antibacterial activities against E. coli and S. aureus.