In the present study, polyvinyl alcohol (PVA) nanofibres having uniformly distributed, well aligned, and highly inter-connected silver nanowires are electrospun. Using the approach, a very high amount of nanowires (up to 34.5 wt%) could be successfully incorporated into the nanofibres. A free standing, highly conducting nanoweb is fabricated with the conductivity of approximately 655 S/cm. These conductive nanowebs are of interest for a number of electronic devices such as sensors or energy storage systems requiring flexibility and high surface area.