The chapter is meant to examine the performance of electrodes blended with nanofibers. This study concerns the synthesis, characterization, and applications of electrodes and polymeric nanofibers. Electrospinning is a basic, simple, and adaptable strategy for creating submicron and nano size filaments. Owing to their enormous surface territory and permeable design, electrospun nanofibers can be utilized widely in biomedical, ecological, defensive attire, and sensors applications. Nano filaments of micron measurement and various compound organizations were prepared. Sensors are set up instruments of synthetic investigation utilized in both electrochemical and optical detecting modes. They permit understanding into ion concentrations in different examples, offering reliable performance. One of the methods of improving this class of sensors is to investigate the advantages of nanoscale receptor layers. In this regard, nanofibers appear to be a profoundly attractive alternative because of novel properties identified with the geometry of this class of nanomaterials. Cyclic voltammetry was applied to examine the changes of behavior of electrodes with various diameters. The result displayed that diameter of nanofibers diminished with decreasing polymer concentration focus and applied voltage and expanding tip-to-collector distance while feeding rate of rate did not have a critical impact on nanofiber diameter. This chapter gives a brief outline of a few electrospun nanofibers applications, focusing on biosensor or nanosensor applications. Here, polymeric nanofibers as an electrode for sensors properties of affectability, selectivity, and identification are fundamentally assessed. Current challenges in this area and prospective future work are likewise discussed.