Polyvinylpyrrolidone (PVP) solutions incorporated with multiwall carbon nanotubes (MWCNTs) were electrospun at various weight percentages, and then the electrical resistance and some thermal properties of these nanocomposite fibers were determined using a high-accuracy electrical resistance measurement device. During the electrospinning process, system and process parameters, such as concentrations, applied voltage, tip-to-collector distance, and pump speeds, were optimized to receive the consistent nanocomposite fibers. When polymers are used in many industrial applications, they require high electrical and thermal conductivities. Most polymers exhibit low electrical conductivity values; however, in the presence of conductive inclusions, the electrical resistance of the MWCNT fibers was reduced from 50 MΩ to below 5 MΩ, which may be attributed to the higher electrical conductivities of these nanoscale inclusions and fewer voids under the applied loads. This study may open up new possibilities in the field for developing electrically conductive novel nanomaterials and devices for various scientific and technological applications.