Effect of a metallo-catalytic cavity flanked by aromatic rings on catalytic dimerization reaction of terminal alkynes is described through a comparison with the model catalysts that weaken the cavity. The di-quinoxaline-spanned resorcin[4]arene provides a definite compartment, where the two Au centers entice two alkynes to carry out a coupling reaction. We newly synthesized two kinds of model compounds in which one lacks two quinoxaline walls and the other has two pyrazine walls, and found that these exhibit much less reactivity. The two quinoxaline moieties proved to be quintessential for the catalytic event.