The fabrication and characterization of nanostructured fibrous gold mats having high specific surface areas is reported. Freestanding porous films of 6–20-μm thickness and density 0.43 ± 0.02 g cm3 are prepared using e-beam evaporation of gold on an electrospun nanoporous polymer template and subsequent removal of the template polymer in a suitable solvent. Structural characterization using electron microscopy techniques shows a nanofiber diameter in the range of 300–6000 nm, and the size of the nanochannels on the fiber surface is ≈200–350 nm. Such surface structuring is achieved through fast evaporation of organic solvent and phase separation of polymers during the electrospinning process. The wedge thickness varies from a few nanometers to a few tens of nanometers. The freestanding films possess good mechanical integrity and robustness. The calculated Young’s modulus based on the slope in the elastic region is ≈114 MPa and gives an ultimate breaking strength of 0.7–0.8 MPa at a percentage elongation of 1.5–2.0%. X-ray diffraction and transmission electron microscopy measurements demonstrate the formation of polycrystalline gold nanostructures. Electrical characterization performed on these gold nanotubes reveals pure metallic behavior. Raman spectroscopic characterization of the fibrous membrane is performed using crystal violet (CV) adsorbed on it. Well-defined spectral peaks are obtainable at concentrations as low as 10−7M of CV, which did not give spectral signals at this low concentration on its own.