Ionophore-doped sensor membranes exhibit greater selectivities and wider measuring ranges when they are prepared with noncoordinating matrixes. Since fluorous phases are the least polar and least polarizable liquid phases known, a fluorous phase was used for this work as the membrane matrix for a series of ionophore-based sensors to explore the ultimate limit of selectivity. Fluorous pH electrode membranes, each comprised of perfluoroperhydrophenanthrene, sodium tetrakis[3,5-bis-(perfluorohexyl)phenyl]borate, and one of four fluorophilic H+-selective ionophores were prepared. All the ionophores are highly fluorinated trialkylamines containing three electron withdrawing perfluoroalkyl groups shielded from the central nitrogen by alkyl spacers of varying lengths: [CF3(CF2)7(CH2)3] 2[CF3(CF2)6CH2]N, [CF3(CF2)7(CH2)3] 2(CF3CH2)N, [CF3(CF 2)7(CH2)3]3N, and [CF3(CF2)7(CH2)5] 3N. Their pKa values in the fluorous matrix are as high as 15.4 ± 0.3, and the corresponding electrodes exhibit logarithmic selectivity coefficients for H+ over K+ as low as <-12.8. The pKa and selectivity follow the trends expected from the degree of shielding and the length of the perfluoroalkyl chains of the ionophores. These electrodes are the first fluorous ionophore-based sensors described in the literature. The selectivities of the sensor containing [CF 3(CF2)7(CH2)5] 3N are not only greater than those of analogous sensors with nonfluorous membranes but were of the same magnitude as the best ionophore-based pH sensors ever reported.