A new approach that combines nanoscale zero-valent iron (nZVI) with electrospinning technology has been put forward to avoid nZVI agglomeration and a secondary pollution. In this study, to enhance the immobilization of nZVI particles onto the polyacrylic acid (PAA)/polyvinyl alcohol (PVA) electrospun nanofiber mat, mats (M1, M2 and M3) with different PAA/PVA mass ratios (1:1, 2:1 and 3:1) were tested for the immobilization of nZVI particles and their performance of removing contaminants. The results indicate that M3 immobilized the most nZVI particles (48.4 wt% on the mat, 2.5 times the figure for previous study) and had the highest removals to methylene blue and Cu(II) ions at 94% and 83.6% respectively, resulting from more free carboxylic groups available on the cross-linked nanofibers as well as a higher porosity into the mat. Therefore, increasing the PAA/PVA ratio is effective to boost the performance of nZVI-PAA/PVA electrospun nanofiber mat, which has a great potential for the application of nZVI-targeted contaminants remediation. (C) 2017 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.