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The conventional approach for preparation of core-sheath fibers is coaxial electrospinning. Single-spinneret electrospinning of emulsions is a much less common method to obtain core-sheath fibers. Core-sheath structure may be generated by electrospinning of homogeneous blend solutions; however, reports on such cases are still scarce. Herein, the preparation of nanofibrous composites from poly(ethylene oxide) (PEO), poly(L-lactide) (PLA) and beeswax (BW) by single-spinneret electrospinning of their homogeneous blend solutions in chloroform is reported. The produced fibers had core/double-sheath structure with a PEO core, PLA inner sheath and BW outer sheath. This original fiber structure was evidenced by transmission electron microscopy, selective extraction of BW or PEO, and X-ray photoelectron spectroscopy. The PLA/BW double sheath led to hydrophobicity of the PEO/PLA/BW mats. The tensile tests revealed that PEO/PLA/BW mats had substantially improved mechanical behavior as compared to PEO, PLA and PEO/BW mats. PEO/PLA/BW mats can be used as drug carriers as evidenced by the one-pot incorporation of the model drug 5-nitro-8-hydroxyquinoline (NQ) into the fibrous materials. Microbiological tests showed that PEO/PLA/BW/NQ had antimicrobial activity. Therefore, the new materials are promising for wound healing applications. [ABSTRACT FROM AUTHOR]