Electrochemistry in supercritical CO(2) (scCO(2)) is difficult because the very low dielectric constant of the fluid restricts the solubility of ionic species and the conductivity of dissolved electrolytes. To overcome this problem to allow us to carry out electrodeposition at macroelectrodes from scCO(2) we have investigated the use of co-solvents and modified electrolyte salts chosen to increase their solubility and dissociation in the supercritical fluid. Here we report results of phase behaviour studies for mixtures of CO(2) with [NBu(n)(4)][BF(4)] and either methanol (CH(3)OH) or acetonitrile (CH(3)CN) as the co-solvent. These show that the solubility of [NBu(n)(4)][BF(4)] is approximately 5 times larger when CH(3)CN is the co-solvent rather than CH(3)OH. Consequently the phase behaviour of the ternary of CO(2)-[NBu(n)(4)][BF(4)]-CH(3)CN was studied in greater detail over a range of compositions. To enhance the conductivity of scCO(2)-CH(3)CN a range of electrolyte salts was synthesised in which the [NBu(n)(4)](+) and/or [BF(4)](-) ion were replaced by different derivatives. Results for the phase behaviour and conductivity of these modified electrolyte salts in scCO(2)-CH(3)CN are reported for several different compositions. We find that increasing the degree of fluorination and size of the ions increases the solubility of the electrolyte salt in scCO(2)-CH(3)CN. Of the 11 electrolytes investigated [NBu(n)(4)][B{3,5-C(6)H(3)(CF(3))(2)}(4)] appears the most suitable for use in scCO(2)-CH(3)CN with a molar conductivity of 22-26 S cm(2) mol(-1) and a maximum measured conductivity of approximately 3 mS cm(-1) for 0.07 M [NBu(n)(4)][B{3,5-C(6)H(3)(CF(3))(2)}(4)] dissolved in scCO(2)-CH(3)CN (molar ratio CH(3)CN : CO(2) approximately 0.12) at 20 MPa and 328.15 K. This is an order of magnitude improvement over similar results for the [NBu(n)(4)][BF(4)] parent. Studies of the conductance as a function of the electrolyte concentration suggest that triple ions make an important contribution to the conductivity of the supercritical fluid.