Three new cis-diquinoxaline spanned cavitands were successfully synthesized. These cis-diphosphinated derivatives were assigned in homogeneous gold-catalyzed dimerization and hydration of alkynes, and rhodium-catalyzed styrene hydroformylation. Results were ranked with those obtained with their trans-diphosphinated isomeric analogues. The structure-activityrelationship employing these two cavitands reveals that the cis- or trans-positioning of the catalyst centers directly influences cooperation between the two metallic atoms to control catalytic activity, reaction profile, and product selectivity. Thus, this comparative study provides us an intellectual basis for future catalytic cavitand chemistry and homogeneous catalysis.