A series of blend nanofiber mats comprising poly(vinyl alcohol) (PVA) and polyurethane (PU) were prepared by dual-jet electrospinning in various parameters. Orthogonal experimental design was used to investigate how those parameters affected on fiber diameters and fiber diameter distribution. Altogether three parameters having three levels each were chosen for this study. The chosen parameters were tip-to-collector distance (TCD), voltage and tip-to-tip distance (TTD). Fiber diameters, thermal properties, mechanical properties and hydrophilicity of the blend nanofiber mats were examined by scanning electron microscopy (SEM), thermogravimetric analysis (TGA), tensile test, contact angle and water absorption test, respectively. The results showed that the optimum conditions for PVA/PU blend nanofiber mats fabricated by dual-jet electrospinning were TCD of 20 cm, voltage of 18 kV and TTD of 4 cm. Besides, the thermal stability of PVA/PU blend nanofiber mats had been improved compared with pure nanofibers. Furthermore, the elongation and tensile strength of the blend nanofiber mats were significantly increased compared with pure PVA and pure PU, respectively. And the blend nanofiber mats exhibited well hydrophilicity.