Electrospinning is a simple and versatile technique for the fabrication of polymeric nanofibrous substrate with high surface to volume ratio. Besides high surface to volume ratio, their dimensional stability and flexibility make it a perfect candidate for conductive network for various sensor applications. Free-Standing conductive network can be fabricated by deposition of PEDOT:PSS or MWCNT through bendable nanofibrous substrate. As a simple example for sensor applications, the moving object has been sensed through the electrostatic interactions between fibers and object. The sensing range has been found to be 1-5 cm above the surface of fabric. By the controlled combination of conductive polymers and electrospun polymer nanofibers effective device miniaturization has been provided without loss of performance. The noncontact motion sensor platform has unique flexibility and light weight holding a potential for wearable sensor technology. For another application as a wearable electronics, the controlled combination of conductive network and light-matter interaction provides opportunities to fabricate photo-resistor exhibits broad band response 400 to 1600 nm that holding promises for ultra-thin sensors used in telecommunication. As a final example, we report the effect of gold and iron oxide nanoparticles on the selectivity and sensitivity of MWCNT or PEDOT:PSS based chemiresistor responsive to VOCs. The interplay between conductive layer by gold and iron oxide nanoparticles resulted a significant conductivity improvement that affecting selectivity which is governed by the interaction between electron-donating VOCs and NP doped conductive layer due to variation in charge carrier densities in conductive layer lattice.