The effect of a metallocatalytic cavity flanked by aromatic rings on the catalytic dimerization of terminal alkynes was explored through a comparison with model catalysts that weakened the cavity. The diquinoxaline‐spanned resorcin[4]arene provided a definite compartment, in which the two Au centers enticed two alkynes to undergo the coupling reaction. We synthesized two kinds of model compounds in which one lacked two quinoxaline walls and the other had two pyrazine walls and found that these catalysts exhibited much lower reactivity. The two quinoxaline moieties proved to be quintessential for the catalytic event.