The unique properties of rubber, along with its diverse applications, have prompted a great deal of interest among researchers to explore advanced multifunctional materials for special purpose applications by incorporating various filler materials into the rubber matrix. This article deals with the application of a relatively new class of materials based on the addition of polytetrafluoroethylene (PTFE) powder to rubber matrixes for preparing PTFE-based elastomeric composites. Besides other properties, the remarkably low friction coefficient of PTFE enables its utilization for tribological applications. However, PTFE in rubbers has not been fully explored, mainly due to its inherent chemical inertness and incompatibility. The present work describes the electron modification of PTFE powder to improve its compatibility with rubber matrixes, the state of the art regarding its application in rubbers, and the preparation of PTFE-based elastomeric composites for tribological applications. It has been demonstrated that, in addition to the improvement in engineering properties, the chemical coupling of modified PTFE powder with rubber matrixes can significantly improve the friction and wear properties of the host elastomer. In addition, a new class of chloroprene composites, with exceptional mechanical and dispersion properties due to chemical coupling of electron-modified PTFE particles and chloroprene rubbers, has been produced. An explanation of the proposed chemical reaction mechanism between the irradiated PTFE and chloroprene rubber, along with a detailed characterization of the compatibility, dispersion, and chemical coupling is presented.