Here we report the successful synthesis, fabrication, and testing of novel asymmetrically substituted 1,3-dialkyl-1,2,3-benzotriazolium-based ionic liquids. Their applicability in energy storage is tested as gel polymer electrolytes (ILGPE) immobilized in poly(vinylidene fluoride-co-hexa-fluoropropylene) (PVDF-HFP) copolymer as a solid-state electrolyte in electric double layer capacitors (EDLC). Asymmetrically substituted 1,3-dialkyl-1,2,3-benzotriazolium salts of tetrafluoroborates (BF₄⁻) and hexafluorophosphates (PF₆⁻) are synthesized by anion exchange metathesis reaction using 1,3-dialkyl-1,2,3-benzotriazolium bromide salts. N-Alkylation followed by quaternization reaction results in dialkyl substitution on 1,2,3-benzotriazole. The synthesized ionic liquids were characterized with ¹H-NMR, ¹³C-NMR, and FTIR spectroscopy. Their electrochemical and thermal properties were studied using cyclic voltammetry, impedance spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The 4.0 V potential windows obtained for asymmetrically substituted 1,3-dialkyl-1,2,3-benzotriazolium salts of BF₄⁻ and PF₆⁻ are promising electrolytes for energy storage. ILGPE tested with symmetrical EDLC with a wide operating window from 0–6.0 V gave an effective specific capacitance of 8.85 F g⁻¹ at a lower scan rate of 2 mV s⁻¹, the energy density of 2.9 μW h and 11.2 mW g⁻¹ power density. The fabricated supercapacitor was employed for lighting red LED (2 V, 20 mA).