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Topography and microstructure engineering are rapidly evolving areas of importance for biomedical and pharmaceutical remits. Here, PVA (Polyvinyl alcohol) microbubbles (diameter range ~126 to 414 μm) were used to fabricate beaded (beads-on) nanofibers using an electrohydrodynamic atomization (EHDA) technique. Mean fiber diameter, inter-bead distance, and aspect ratio (AR) were investigated by regulating EHDA process parameters. PVA fibers (diameter range ~233 to 737 nm) were obtained possessing bead ARs in the range of ~10 to 56%. AR was used to modulate hydrophilicity and active release.