The design and fabrication of three-dimensional (3D) nanostructures with fascinating SERS performance have drawn much attention in the field of materials science and nanotechnology. In this work, 3D poly (acrylic acid) (PAA)/poly (vinyl alcohol) (PVA) nanofibrous membrane was used as templates for the electrostatic assembly of gold nanoparticles. The PAA/PVA electrospun nanofibers were crosslinked using a simple thermal treatment, which would prevent the nanofibers from dissolution in the nanoparticle solution. It was found that the gold nanoparticles were uniformly immobilized on the nanofibers, causing high reproducibility of this SERS substrate. The nanocomposite membrane also showed high sensibility for the detection of trace amount of analytes such as 4-aminothiophenol and Rhodamibe 6G. (C) 2017 Elsevier B.V. All rights reserved.