Electrochemical energy storage is a very active research topic. However, the use of liquid electrolyte in such systems as supercacitors presents several drawbacks on security and packaging. One way to overcome these issues is to design supercapacitors using solid-state electrolytes. We report here the one-pot synthesis and the characterization of self-standing gel polymer electrolyte (SGPE) composed of semi-Interpenetrating Polymer Networks (semi-IPN) based on poly(ethylene oxide) (PEO) network and non cross-linked nitrile butadiene rubber (NBR), self-containing EMITFSI/γ-Butyrolactone (50/50 wt%/wt%) binary mixtures. The SGPE under the form of a thin film are then used as solid electrolyte and also as separator in supercapacitors with Single Wall Carbon Nanotubes (SWCNTs) bucky paper as electrodes. Thermal characterization revealed the suitability of all synthesized membrane in wide range of operating temperature. Electrochemical stabilities of SGPE were close to that of a cellulose separator system (ESW∼3.2–3.6 V) at 20 °C, and were relatively higher than a cellulose system at 100 °C: 2.1–2.5 V and 1.8 V respectively. Furthermore, floating experiments at 100 °C (holding voltage at 2 V) revealed the exceptionally high stability of SGPE, with a residual capacitance of 93% after 500 h. This high electrochemical performance demonstrated the potential of semi-IPN SGPE as separator/electrolyte for high performance supercapacitors.