The present article reports the spectroscopic investigations on non-covalent interaction of fullerenes C₆₀ and C₇₀ with a macrocyclic receptor molecule, namely, 1,3,5,7-tetrahomo-p-tert-butylcalix[8]arene (1) in toluene. Jobs method of continuous variation reveals 1:1 stoichiometry for the fullerene complexes of 1.The most fascinating feature of the present study is that 1 binds selectively C₆₀ compared to C₇₀ as obtained from binding constant (K) data of C₆₀-1 (K_C60-1) and C₇₀-1 (K_C70-1) complexes which are enumerated to be 265,000 dm³ mol⁻¹ and 63,430 dm³ mol⁻¹, respectively, and selectivity in binding (K_C60-1/K_C70-1) is estimated to be 4.18 as obtained from UV–Vis study. Steady state fluorescence studies reveal quenching of fluorescence of 1 in presence of fullerenes and the K value of the C₆₀-1 and C₇₀-1 complexes are estimated to be 80,760 and 68,780 dm³ mol⁻¹, respectively, with selectivity in binding (K_C60-1/K_C70-1) ~1.18. ¹H NMR analysis provides very good support in favor of strong binding between C₆₀ and 1. The high value of K value for C₆₀-1 complex indicates that 1 forms an inclusion complex with C₆₀.