Electrospinning was employed to prepare new multi-functional nanowebs. Cyclodextrin based inclusion complex (CD-IC) was used to disperse multiwalled carbon nanotubes (MWNT) within electrospun polyvinylidene fluoride nanofibrous membranes (PVdF-NFM). Subsequently, MWNT(CD-IC)/PVdF-NFM was loaded with gold (Au) particles. The morphology, structure and thermal properties of Au/MWNT(CD-IC)/PVdF-NFM were investigated by transmission electron microscopy, field emission scanning electron microscopy, FT-IR spectroscopy, x-ray diffraction spectroscopy and differential scanning calorimetry. The new Au/MWNT(CD-IC)/PVdF-NFM is electroactive and shows excellent electrocatalytic activity towards oxidation of ascorbic acid.