We describe the first synthesis of the novel meso-pentaspirocyclohexyl calix [5] pyrrole 2b. Anion–guest properties of the new compound were evaluated with respect to fluoride, chloride, and bromide tetrabutylammonium salts by 1H NMR titration techniques in deuterated dichloromethane at 22° C by following the induced shifts in the NH resonances upon complexation.