The accurate interaction energies of the CH/π interaction in the benzene-X clusters (X = ethylene and acetylene) were experimentally and theoretically determined. Two-color multiphoton ionization spectroscopy was applied, and the binding energies in the neutral ground state of the clusters were evaluated from the dissociation threshold measurements of the cluster cations. The experimental binding energies of the clusters (D₀) were 1.4 ± 0.2 and 2.7 ± 0.2 kcal/mol, respectively. Estimated CCSD(T) interaction energies for the clusters at the basis set limit (D_e) were 2.2 and 2.8 kcal/mol, respectively. Calculated D₀ values (1.7 and 2.4 kcal/mol, respectively) are close to the experimental values. Large electron correlation contributions (E_corr = -3.6 and -2.8 kcal/mol, respectively) show that dispersion is the major source of the attraction in both clusters. The electrostatic interaction in the ethylene cluster is very small (-0.38 kcal/mol), as in the case of the benzene-methane cluster, whereas the electrostatic interaction in the acetylene cluster is large (-1.70 kcal/mol). The shifts of the S₁-S₀ transition also suggest that the ethylene cluster is a van der Waals-type cluster, but the acetylene cluster is a π-hydrogen-bonded cluster. The nature of the CH/π interaction of the "activated" alkyne C-H bond is significantly different from that of the "nonactivated" (or typical) alkane and alkene C-H bonds.