In this study, we have introduced electrospinning of a colloidal solution rather than the conventional sol-gel process as a novel strategy to produce silver nanofibres. Typically, a silver acetate/polyvinyl alcohol colloidal solution was successfully electrospun. Electrophoretic light scattering (ELS) and dynamic light scattering (DLS) analyses have affirmed that the electrospun solution is a colloid with a zeta-potential of -2 mV and average particle diameter of 373 +/- 1 nm. Moreover, FTIR analysis affirmed that neither the polymer nor silver acetate nanoparticles were affected during the electrospinning process. Calcination of the electrospun mats at 700 degrees C in an argon atmosphere produced smooth and unbroken pure silver nanofibres. Surface plasmon resonance of the resultant silver nanofibres was detected at 962 nm which is biologically beneficial. Furthermore, the synthesised silver nanofibres revealed thermal hysteresis in the electrical conductivity properties. These advantageous physical features strongly suggest utilising the prepared nanofibres in various fields.