Modified natural rubber (NR) polymer hosts having low transition glass temperatures have been investigated. Three types of modified NR, namely 25% epoxidised NR (ENR-25), 50% ENR (ENR-50) and polymethyl methacrylate grafted NR (MG-49) were employed. Results are reported for ionic conductivity and thermal properties for both unplasticised and plasticised polymer electrolyte systems. The samples were in the form of free standing films with the thickness 0.2–0.5mm and mixtures of ethylene carbonate (EC) and propylene carbonate (PC) were used as plasticisers. Unplasticised modified NR based systems exhibit ionic conductivities in 10−6–10−5 Scm−1 range at ambient temperatures. Incorporating 50–100% of EC/PC by weight to the systems yielded mechanically stable films and ionic conductivities in 10−4–10−3 Scm−1 range at ambient temperature. The thermal event of the systems has displayed an increasing trend of transition glass temperature at elevated salt concentration whereas incorporation of EC and PC into the systems leads to marked reduction in their T g values.