Theoretical studies of a new ion-pair receptor, meso-octamethylcalix[4]pyrrole (OMCP), and its interactions with the halide anions F(-), Cl(-), and Br(-) and the cesium halides CsF, CsCl, and CsBr have been performed. Geometries, binding energies, and binding enthalpies were evaluated with the restricted hybrid Becke three-parameter exchange functional (B3LYP) method using the 6-31+G(d) basis set and relativistic effective core potentials. The optimized geometric structures were used to perform natural bond orbital (NBO) analysis. The two typical types of hydrogen bonds, N-H…X(-) and C-H…X(-), were investigated. The results indicate that hydrogen bonding interactions are dominant, and that the halide anions (F(-), Cl(-), and Br(-)) offer lone pair electrons to the σ*(N-H) or σ*(C-H) antibonding orbitals of OMCP. In addition, electrostatic interactions between the lone pair electrons of the halide anion and the LP* orbitals of Cs(+) as well as cation-π interactions between the metal ion and π-orbitals of the pyrrole rings have important roles to play in the Cs(+)•OMCP•X(-) complexes. The current study further demonstrates that this easy-to-make OMCP host compound functions as not only an anion receptor but also an ion-pair receptor.