This article is portion of a comprehensive study on the development of nanofiber-reinforced polymer composites for electrostatic discharge materials and structural composites. Vapor-grown carbon fibers with an average diameter of 100 nm were used as a precursor and model fiber system for carbon nanotubes. These nanofibers were purified and functionalized to provide for an open network of high-purity nanofibers. Banbury-type mixing was used to disperse the nanofibers in the polymer matrix. Rheological and microscopic analysis showed that the high shear processing of the polymer/nanofiber mixture led to a homogeneous dispersion of nanofibers with no agglomerates present and no shortening of the nanofibers. The shear thinning behavior of polymeric materials helps in the mixing of the nanofibers to form the composites. A percolation threshold for electrical conduction of 9-18 wt % was observed for the highly dispersed nanofiber networks. The electrical behavior of these materials was not affected by changes in humidity. Microscopic analysis showed highly dispersed nanofibers with no indications of porosity. These conducting polymers are well suited for electrostatic discharge applications, and might well become multifunctional materials for strength/electrical applications.