A new gel polymer electrolyte (GPE) based supercapacitor with an ionic conductivity up to 0.32–0.94 mS cm−2 has been synthesized from a mixture of an ionic liquid (IL) with nanocellulose (NC). The new NC-ionogel was prepared by combining the IL 1-ethyl-3-methylimidazolium dimethyl phosphate (EMIMP) with carboxymethylated cellulose nanofibers (CNFc) at different ratios (CNFc ratio from 1 to 4). The addition of CNFc improved the ionogel properties to become easily printable onto the electrode surface. The new GPE based supercapacitor cell showed good electrochemical performance with specific capacitance of 160 F g−1 and an equivalent series resistance (ESR) of 10.2 Ω cm−2 at a current density of 1 mA cm−2. The accessibility to the full capacitance of the device is demonstrated after the addition of CNFc in EMIMP compared to the pristine EMIMP (99 F g−1 and 14.7 Ω cm−2).