Nanomaterials, including nanofibers, are used for various healthcare applications, including sensors, wearable textiles, and biomedical devices. In this dissertation, electrospinning was used to fabricate nanofibers using a conductive polymer named poly(3,4-ethylenedioxythiophene) (PEDOT). Unfortunately, the use of PEDOT is often limited by the acidic nature of polystyrene sulfonate (PSS), a common dispersant for PEDOT. For this reason, we investigated the impact of increasing the pH value of PEDOT:PSS/polyvinyl alcohol (PVA) precursors on the morphological and electrical properties of the resultant as-spun fibers. We discovered that neutral and even slightly basic PEDOT:PSS/PVA precursors could be electrospun without impacting the resultant electrical properties suggesting their potential for use in wearable textiles and sensors. A second major direction of this dissertation was the investigation of oligopeptide-based nanofibers. We successfully electrospun pure oligopeptide-based fibers despite their low molecular weight. Based on their ability to form fibers, we proposed a hypothesis that electrospinnable oligopeptides self-assemble despite the dispersive nature of the solvent used (1,1,1,3,3,3 hexafluoro-2-propanol, HFIP). The intermolecular interactions between self-assembled structures at sufficiently high concentrations facilitate electrospinning. Fourier-transform infrared (FTIR) spectroscopy and microrheology results support this hypothesis. The results from this fundamental study on oligopeptides hold the potential to be extended to other self-assembling small molecules. In addition to the previously mentioned major directions of this dissertation, the electrospinning of polydimethylsiloxane (PDMS) fibers was explored, as were peptide hydrogels and their ability to serve as humidity sensors. These studies suggest that electrospun fiber mats can be used for wearable electronics, flexible humidity sensors, and functional biomaterials.