A cross-linked microfibrous anion exchange membrane with high ion permselectivity and robust mechanical properties was fabricated by electrospinning. Copolymer, poly N, N-dimethylaminoethyl methacrylate (DMAEMA)-co-2-hydroxyethyl methacrylate (HEMA), was selected as the electrospun material. Fourier transform infrared (FTIR) spectroscopy, (HNMR)-H-1 and scanning electron microscopy (SEM) were employed to characterize the copolymer and microfibrous mat. The electrospinning optimal parameters were determined by orthogonal experiments. Formaldehyde vapor was applied to crosslink the mat. It was observed that the water sorption decreased from 75.7% to 30.4% as the crosslinking time increased from 20 h to 32 h. The robust mat with the high tensile strength of 4.62 MPa and 50% elongation at break was obtained at 24 h. The ion permeability of NO3-, Cl-, SO42- were 94, 91 and 87%.