Ground state non-covalent interactions between a newly designed macrocyclic 1,3,5-trihomo calix[6]arene receptor, designated as 1, and the C₆₀ and C₇₀ fullerenes have been studied in toluene solutions. It was observed that the absorbances of both C₆₀ and C₇₀ solutions increased upon the addition of increasing concentrations of compound 1. Job’s method of continuous variation established 1:1 stoichiometry for these fullerene-1 complexes. The binding constant (K) data reveal that compound 1 binds to C₇₀ more strongly compared to C₆₀, i.e., _KC60-1 = 230 dm³·mol⁻¹ and K_C70-1 = 517 dm³·mol⁻¹. Proton NMR analysis provides very good support for strong binding between C₇₀ and 1. Estimations of the solvent reorganization energy (RS) suggest that the C70-1 complex is stabilized more than the corresponding C₆₀-1 complex, with R_S(C60-1) =−1.970 eV and R_S(C70-1) =−2.300 eV. Molecular mechanics force field method calculations established that the binding pattern of C₇₀ towards 1 occurs in the side-on rather than end-on orientation, and that the C₇₀-1 complex gains 5.23 kJ·mol⁻¹ of extra stabilization energy with this side-on geometrical arrangement.