In this paper, we report on thermophysical and electrochemical investigations of a series of molecular solvent/ionic liquid (IL) binary mixture electrolytes. Tetraethylene glycol dimethyl ether (TEGDME) is utilized as the molecular solvent component in separate mixtures with two bis{(trifluoromethyl)sulfonyl}imide anion based ILs paired with similarly sized cyclic and acyclic alkylammonium cations; 1-butyl-1-methylpyrrolidinium bis{(trifluoromethyl)sulfonyl}imide, [Pyrr 14 ] [TFSI], or N-butyl-N,N-dimethyl-N-ethylammonium bis{(trifluoromethyl)sulfonyl}imide, [N 1124 ] [TFSI]. The blending of ILs with select molecular solvents is an important strategy for the improvement of the typically sluggish transport capabilities of these interesting electrolytic solvents. Bulk volumetric and transport properties are reported as a function of temperature and binary mixture formulation; demonstrating the capacity for enhancing desired properties of the IL. Micro-disk electrode voltammetry and chronoamperometry in O 2 -saturated binary mixture electrolytes was used to assess the effect of formulation on the solubility and diffusivity of the dissolved gas. In addition, further investigations of the behavior of the O 2 redox couple at a GC macro-disk electrode are discussed. The exploration of ionic liquids (ILs) as alternatives to conventional molecular solvents in electrolyte formulations is continually growing for a variety of electrochemical applications. These low melting organic salts can be tailored to exhibit a variety of properties, including hydrophobicity and thermal, chemical, and electrochemical stability, which make them attractive candidate electrolyte solvents. Composed solely of ionic components, ILs consequently possess intrinsic electrolytic conductivity and are additionally non-volatile. These properties have encouraged the use of ILs as (complete or partial) substitutions of the volatile components of commercial Li-ion batteries, electrochemical double layer capacitors (EDLCs), and other prospective battery technologies (e.g. Na-ion, Mg-ion and metal-air batteries) for the development of potentially safer devices.1-15 Furthermore, the high (electro)chemical stabilities and non-volatilities exhibited by many IL structures provides interesting electrolyte media for electrochemical gas sensors (e.g. for O 2 , 16-19 CO 2 , 20,21 NO 2 22 ) where traditional solvents are prone to evaporation leading to device failure, and also for electromechanical actuator, 23-25 and electrodeposition applications. [26][27][28] Nevertheless, while the properties of ILs are dependent on the virtually unlimited combinations of different cation and anion structures, the attractive features are generally coupled with sluggish transport properties relative to conventional electrolytes based on either aqueous or organic solvents. In turn, electrochemical devices constructed with neat IL electrolytes are likely to suffer transport limitations on useable current rates for the given application, for example restricting power capabiliti...