The electrical characteristics of polymer nanocomposites incorporating rod-like nanofillers are briefly discussed in this chapter. A lot of interest has been paid to polymer nanocomposites containing rod-like nanofillers because of their distinct electrical characteristics and possible use in many different domains. Flexible electronics, sensors, energy storage, and electromagnetic shielding are just a few of the new possibilities made possible by the electrical properties of polymer nanocomposites with rod-like nanofillers. The distribution and alignment of rod-like nanofillers inside the polymer matrix have a significant impact on the electrical behavior of polymer nanocomposites. These nanofillers may be effectively dispersed and aligned to form percolation networks, which will facilitate charge transport channels and increase electrical conductivity. One of the major benefits of rod-like nanofillers is their high aspect ratio, which makes it easier to build conductive networks inside the polymer matrix. This network formation makes it simpler to generate efficient charge transport channels than neat polymers, which enhances electrical conductivity. The electrical performance of the nanocomposite is enhanced by the multiple pathways for electron or ion transport provided by the firmly connected nanofillers. The concentration, aspect ratio, and dispersion of the nanofiller within the polymer matrix can all be changed to alter the electrical conductivity of polymer nanocomposites. With the proper choice and modification of these parameters, a wide range of electrical conductivity values, from insulating to highly conductive regimes, can be obtained. Additionally, the electrical characteristics are greatly influenced by the interfacial contacts between the rod-like nanofillers and the polymer matrix. The interfacial adhesion and enhanced charge transfer between the nanofillers and the polymer matrix can be improved by surface modifications of the nanofillers or chemical compatibilizers. Furthermore, adding rod-shaped nanofillers to polymer matrices improves dielectric characteristics, mechanical strength, thermal stability, etc.