In this paper, we report for the first time the successful formation of a covalent cross-linking structure between polyacrylic acid and polyamide 66 in an electrospun nanofiber membrane by the facilitated amidation reaction using N-Hydroxy-succinimide (NHS) and N-(3-Dimethylaminopropyl)-N’-ethyl-carbodiimide hydrochloride (EDC). The structure and properties of the fiber membrane are characterized using scanning electron microscopy, wide field X-ray diffraction and differential scanning calorimetry. The results show that the presence of the cross-linked structure not only affects the construction of the nanofiber network framework but also influences the pore size distribution and size of the fiber membrane surface, which in turn affects its retention of contaminants and water absorption performance. After modification, the cross-linked membranes exhibited a significant retention performance of up to 77% for methyl tert-butyl ether (MTBE) with a reduced pure water flux. Furthermore, after crosslinking, the fiber membrane has been strongly enhanced with more stable pH response behavior.