The exploitation of epoxidized natural rubber (ENR) in electrochemical applications is approaching its limits because of its poor thermo-mechanical properties. These properties could be improved by chemical and/or physical modification, including grafting and/or crosslinking techniques. In this work, acrylonitrile (ACN) has been successfully grafted onto ENR- 25 by a radical photopolymerization technique. The effect of (ACN to ENR) mole ratios on chemical structure and interaction, thermo-mechanical behaviour and that related to the viscoelastic properties of the polymer was investigated. The existence of the –C≡N functional group at the end-product of ACN-g-ENR is confirmed by infrared (FT-IR) and nuclear magnetic resonance (NMR) analyses. An enhanced grafting efficiency (~57%) was obtained after ACN was grafted onto the isoprene unit of ENR- 25 and showing a significant improvement in thermal stability and dielectric properties. The viscoelastic behaviour of the sample analysis showed an increase of storage modulus up to 150 × 10³ MPa and the temperature of glass transition (T_g) was between −40 and 10 °C. The loss modulus, relaxation process, and tan delta were also described. Overall, the ACN-g-ENR shows a distinctive improvement in characteristics compared to ENR and can be widely used in many applications where natural rubber is used but improved thermal and mechanical properties are required. Likewise, it may also be used in electronic applications, for example, as a polymer electrolyte in batteries or supercapacitor.