High-voltage (≥4.0 V) operation of supercapacitor devices was demonstrated using carbon nanotubes as active electrode materials combined with room temperature ionic liquids as electrolyte. Pouch cells were assembled with four different ionic liquids, 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF4), diethyl-N-methyl-N-(2-methoxyethyl) ammonium bis(trifluoromethanesulfonyl)imide (DEME-TFSI), diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate (DEME-BF4), and 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14-TFSI). Cyclic voltammetry showed the maximum operational voltage to be 4.5 V for DEME-TFSI and 4.7 V for DEME-BF4. Compared to electric double layer capacitor (EDLC) cells using propylene carbonate electrolyte at 2.7 V, capacitance increased by 20% using BMIM-BF4 at 4.0 V, DEME-TFSI at 4.5 V, DEME-BF4 at 4.7 V, and Pyr14-TFSI at 4.3 V, with tripling of energy density and comparable power density using Pyr14-TFSI-based EDLCs. Long-term cyclability using BMIM-BF4 ionic liquid electrolyte operating at 4.0 V showed retention of >80% of initial capacitance after 65,000 continuous cycles without doubling of initial cell equivalent series resistance.