The purpose of this work was to characterise supercritical hydrofluorocarbons (HFC) that can be used as solvents for electrodeposition. The phase behaviour of CHF(3), CH(2)F(2), and CH(2)FCF(3) containing [NBu(n)(4)][BF(4)], [NBu(n)(4)][B{3,5-C(6)H(3)(CF(3))(2)}(4)] and Na[B{3,5-C(6)H(3)(CF(3))(2)}(4)] was studied and the conditions for forming a single supercritical phase established. Although all three HFCs are good solvents for [NBu(n)(4)][BF(4)] the results show that the CH(2)F(2) system has the lowest p(r) for dissolving a given amount of [NBu(n)(4)][BF(4)]. The solubility of Na[B{3,5-C(6)H(3)(CF(3))(2)}(4)] in CH(2)F(2) was found to be unexpectedly high. Studies of the phase behaviour of CH(2)F(2) containing [NBu(n)(4)][BF(4)] and [Cu(CH(3)CN)(4)][BF(4)] showed that the copper complex was unstable in the absence of CH(3)CN. For CHF(3), [Cu(hfac)(2)] was more soluble and more stable than [Cu(CH(3)CN)(4)][BF(4)] and only increased the phase-separation pressure by a moderate amount. Studies of the conductivity of [NBu(n)(4)][B(C(6)F(5))(4)], [NBu(n)(4)][B{3,5-C(6)H(3)(CF(3))(2)}(4)], [NR(f)Bu(n)(3)][B{3,5-C(6)H(3)(CF(3))(2)}(4)] (R(f) = (CH(2))(3)C(7)F(15)), and Na[B{3,5-C(6)H(3)(CF(3))(2)}(4)] were carried out in scCH(2)F(2). The results show that these salts are more conducting than [NBu(n)(4)][BF(4)] under the same conditions although the increase is much less significant than that reported in previous work in supercritical CO(2) + CH(3)CN. Consequently, either [NBu(n)(4)][BF(4)] or the corresponding BARF salts would be suitable background electrolytes for electrodeposition from scCH(2)F(2).