Attaining meticulous dominion over the binding milieu of catalytic metal sites remains an indispensable pursuit to tailor product selectivity and elevate catalytic activity. By harnessing the distinctive attributes of a Zr4+-anchored thiacalix[4]arene (TC4A) metalloligand, we have pioneered a methodology for incorporating catalytic Ag1+ sites, resulting in the first Zr-Ag bimetallic cluster, Zr2Ag7, which unveils a dualistic configuration embodying twin substructures linked by an moiety. This cluster unveils a trinity of discrete Ag sites: a pair ensconced within the subunits, and one located between the two units. Expanding the purview, we have also crafted the ZrAg3 and Zr2Ag2 clusters, meticulously mimicking the two Ag site environment inherent in the monomer. The distinct structural profiles of Zr2Ag7, ZrAg3, and Zr2Ag2 provide an exquisite foundation for a precise comparative appraisal of catalytic prowess across the three Ag sites intrinsic to Zr2Ag7. Remarkably, Zr2Ag7 eclipses its counterparts in the electroreduction of CO2, culminating in an CO faradaic efficiency (FECO) of 90.23% at -0.9 V. This achievement markedly surpasses the performance metrics of ZrAg3 (FECO: 55.45% at -1.0 V) and Zr2Ag2 (FECO:13.09% at -1.0 V). Utilizing in situ ATR-FTIR, we can observe the reaction intermediates on the Ag sites. To unveil the underlying mechanisms, we employ density functional theory (DFT) calculations to determine the changes in free energy accompanying each elementary step throughout the conversion of CO2 to CO. Our findings reveal the exceptional proficiency of the bridged-Ag site that interconnects the paired units, skillfully stabilizing *COOH intermediates, surpassing the stabilization efficacy of the other Ag sites located elsewhere. The invaluable insights gleaned from this pioneering endeavor lay a novel course for the design of exceptionally efficient catalysts tailored for CO2 reduction reactions, emphatically underscoring the novel vistas this research unshrouds.