Hollow fiber composite (HFC) nanofiltration (NF) membrane demonstrates significant commercial potential profiting from its self-supporting characteristic, high packing density and strong fouling resistance. In this work, a high-performance HFC NF membrane was successfully developed through simultaneous modification of the substrate via alkaline hydrolysis and incorporation of iopamidol (IPD) into the selective layer. Alkaline hydrolysis enhanced the hydrophilicity of the polyacrylonitrile (PAN) substrate by converting –CN groups into –COOH, thereby sharply improving the success rate of HFC NF membrane fabrication. The addition of IPD into piperazine (PIP) solution effectively increased the water permeability of the HFC NF membrane without compromising its salt rejection. Specifically, the optimized membrane sample denoted as NF-0.15P + 0.5I with 0.5 w/v% IPD added demonstrated a 44 % increase in PWP from 21.8 L·m−2·h−1·bar−1 to 31.5 L·m−2·h−1·bar−1, while maintaining a Na2SO4 rejection over 96.8 %. This improvement can be attributed to the decreased selective layer thickness and reduced MWCO. Furthermore, the membrane exhibited exceptional dye/salt separation performance. This work represents a novel approach leading to the development of a HFC NF membrane suitable for dye/salt separation.