The present paper reports the spectroscopic investigations on non-covalent interaction of fullerenes C₆₀ and C₇₀ with a designed trihomocalix[6]arene (2) in toluene. UV–vis studies reveal appreciable ground state interaction between fullerenes and 2. Jobs method of continuous variation establishes 1:1 stoichiometry for fullerene–2 complexes. Binding constant (K) data reveals that 2 binds C₇₀ more strongly compared to C₆₀, i.e. K_C60–2 = 47,540 dm³ mol⁻¹ and K_C70–2 = 86,360 dm³ mol⁻¹. Proton NMR studies provide very good support in favor of strong binding between C₇₀ and 2. Estimation of solvent reorganization energy (RS) evokes that C_70–2 complex is stabilized more compared to C₆₀–2 complex as R_S(C60–2) = −1.162 eV and R_S(C70–2) = −1.244 eV. Semiempirical calculations at third parametric level of theory in vacuo evoke the single projection structures of the fullerene–2 complexes and interpret the stability difference between C₆₀ and C₇₀ complexes of 2 in terms of enthalpies of formation values.