Despite the widespread use of perfluorinated solvents with amino and ether groups in a variety of application fields, the coordinative properties of these compounds are poorly known. It is generally assumed that the electron withdrawing perfluorinated moieties render these functional groups rather inert, but little is known quantitatively about the extent of their inertness. This paper reports on the interactions between inorganic monocations and perfluorotripentylamine and 2H-perfluoro-5,8,11-trimethyl-3,6,9,12-tetraoxapentadecane, as determined with fluorous liquid-membrane cation-selective electrodes doped with tetrakis[3,5-bis(perfluorohexyl)phenyl]borate salts. The amine does not undergo measurable association with any ion tested, and its formal pK(a) is shown to be smaller than -0.5. This is consistent with the nearly planar structure of the amine at its nitrogen center, as obtained with density functional theory calculations. The tetraether interacts very weakly with Na+ and Li+. Assuming 1:1 stoichiometry, formal association constants were determined to be 2.3 and 1.5 M-1, respectively. This disproves an earlier proposition that the Lewis base character in such compounds may be nonexistent. Due to the extremely low polarity of fluorous solvents and the resulting high extent of ion pair formation, a fluorophilic electrolyte salt with perfluoroalkyl substituents on both the cation and the anion had to be developed for these experiments. In its pure form, this first fluorophilic electrolyte salt is an ionic liquid with a glass transition temperature, T-g, of -18.5 degrees C. Interestingly, the molar conductivity of solutions of this salt increases very steeply in the high concentration range, making it a particularly effective electrolyte salt.