Room temperature ionic liquids exhibit unusual and, for electrochemical applications, promising properties such as ionic conductivity and non-volatility. Microdroplet and thin film deposits of an ionic liquid, 1-methyl-3-(2,6-(S)-dimethylocten-2-yl)-imidazolium tetrafluoroborate (MDIM+BF4 −) on electrode surfaces are studied in order to assess the ability of aqueous ions to partition into the ionic liquid. Two complementary methodologies, deposition of ionic liquid onto a 4.9 mm diameter basal plane pyrolytic graphite electrode followed by voltammetric analysis and casting of an ionic liquid film onto a random array of 7 μm diameter carbon microelectrodes (RAMTM electrode) followed by chronoamperometry, are employed. The ability of hydrophilic ions to partition from the water phase into the ionic liquid phase is unexpected and is shown to depend strongly on (i) the type of ion, (ii) specific interaction of the ion with the ionic liquid, and (iii) the concentration of the supporting electrolyte. Voltammetric responses obtained for the reduction of Fe(CN)6 3− partitioned into microdroplet and thin film deposits of MDIM+BF4 − indicate selective uptake of ferricyanide into the ionic liquid phase. Chronoamperometric experiments at RAMTM electrodes are used to quantify both the concentration of Fe(CN)6 3− in the ionic liquid and the diffusion coefficient.