A simple electrolyte consisting of NaPF6 salt in 1,2-dimethoxyethane (DME) can extend the voltage window of electric double-layer capacitors (EDLCs) to >3.5 V. DME does not passivate carbon electrodes at very negative potentials (near Na/Na+), extending the practical voltage window by about 1.0 V compared to standard, non-aqueous electrolytes based on acetonitrile. The voltage window is demonstrated in two-and three-electrode cells using a combination of electrochemical impedance spectroscopy (EIS), charge-discharge cycling, and measurements of leakage current. DME-based electrolytes cannot match the high conductivity of acetonitrile solutions, but they can satisfy applications that demand high energy density at moderate power. The conductivity of NaPF6 in DME is comparable to commercial lithium-ion battery electrolytes and superior to most ionic liquids. Factors that limit the voltage window and EDLC energy density are discussed, and strategies to further boost energy density are proposed. (C) 2016 The Electrochemical Society.