Electrospinning of biopolymers, such as proteins and polysaccharides, has recently attracted much attention for the fabrication of scaffolds for tissue engineering. In this report, zein/hyaluronic acid (HA) blend fibrous membranes were electrospun and characterized. To facilitate the compatibility of zein and HA, poly(vinyl pyrrolidone) (PVP) was introduced into aqueous ethanol solutions of the blend. A series of zein/HA/PVP blend fibrous membranes with different volume ratios were successfully electrospun. The effect of blend composition on the morphology of electrospun fibrous membranes was investigated by scanning electron microscopy. The average diameter of blend fibers increased with increasing the content of zein component. The electrospun zein/HA/PVP fibrous membranes were then cross-linked by methylene diphenyl diisocyanate (MDI). The morphology of the cross-linked zein/HA/PVP fibrous membranes changed slightly compared with un-cross-linked membranes. Tensile tests demonstrated that the mechanical properties of the zein/HA/PVP fibrous membranes were improved by cross-linking.