After the addition of a surface-active agent, sodium dodecyl benzene sulfonate (SDBS), electrospun polyvinyl alcohol (PVA) nanofibres showed a significant enhancement in the mechanical properties, such as improved tensile strength and elongation at break. The improved crystallinity and strong intermolecular hydrogen bonds between the molecules of SDBS and PVA were the two main factors that improved the mechanical properties. In addition, a sharp decrease in surface tension of PVA solution with the addition of SDBS was observed, and the protruding droplet at the tip of needle diminished in the electrospinning process.