Tris(2-aminoethyl)amine (tren) based pentafluorophenyl-substituted tripodal L, tris[[(2,3,4,5,6-pentafluorobenzyl)amino]ethyl]amine receptor is synthesized in good yield and characterized by single crystal X-ray diffraction analysis. Detailed structural aspects of binding of different anionic guests toward L in its triprotonated form are examined thoroughly. Crystallographic results show binding of fluoride in the C-3v-symmetric cavity of [H3L](3+) where spherical anion fluoride is in tricoordinated geometry via (N-H)(+)center dot center dot center dot F interaction in the complex [H3L(F)]center dot[F](2)center dot 2H(2)O, (3). In the case of complexes [H3L(OTs)]center dot[OTs](2), (4) and [H3L(OTs)]center dot[NO3]center dot[OTs], (5), tetrahedral p-toluenesulphonate ion is engulfed in the cavity of [H3L](3+) via (N-H)center dot center dot center dot O interactions. Interestingly, complex [(H3L)(2)(SiF6)]center dot[BF4](4)center dot CH3OH center dot H2O, (6) shows encapsulation of octahedral hexafluorosilicate in the dixneric capsular assembly of two [H3L](3+) units, via a number of (N-H)(+)center dot center dot center dot P interactions. The kinetic parameters of L upon binding with different anions are evaluated using a potentiometric study in solution state. The potentiometric titration experiments in a polar protic methanol/water (1:1 v/v) binary solvent system show high affinity of the receptor toward more basic fluoride and acetate anions, with a lesser affinity for other inorganic anions (e.g., chloride, bromide, nitrate, sulfate, dihydrogenphosphate, and p-toluenesulphonate).