Exposing polytetrafluoroethylene (PTFE) to irradiation brings about significant alterations in both its crystallinity and conductivity. The primary objective of this study is to investigate the connection, if any, between crystallinity, a structural feature, and electrical conductivity, which represents a macroscopic property. This was accomplished by subjecting PTFE to varying doses of γ-rays, reaching up to 200 kGy. Various physicochemical characterizations were conducted to elucidate the impact of irradiation on dielectric properties. We show that irradiation produces chain scission and oxidized groups at chain ends. The material becomes more crystallizable after irradiation whereas the increase in conductivity would result from transport due to oxidized groups and short chain formation.