The present study reports the electrospinning of commercially available polyaniline-carbon black composite to develop conductive nanofibrous mats using polyvinyl alcohol as a binder solution. This binder solution was sublimated at 230 degrees C to attain a complete conducting nanofiber network. The binder sublimation was confirmed using therm gravimetric analysis (TGA). Ultra-violet visible spectroscopy was used to determine the refractive index values for porosity measurements. It was observed that the heat treatment reduced the fiber diameter from similar to 250 nm to similar to 160 nm and increased the porosity from 41 +/- 1.2% to 70 +/- 2%. The spatial specific conductance mapping using Scanning Electro-Chemical Microscopy showed that the presence of polyvinyl alcohol binder in polyaniline-carbon black composite could introduce percolation threshold. The heat-treated fibers showed four times increase in specific conductance values on removal of binder phase from the fiber structure. The role of nanoscaled Schottky barriers in determining conductive pathways through polymer by hopping mechanism and also along carbon black particles are also been proposed in this study.