Many challenging chemical reactions require precious metal catalysts to proceed. Our research group develops main-group metalloligands (Groups 13 and 14) as an electronic lever for tuning a reactive transition metal active site via a direct metal–metal interaction. This approach has allowed for the development and optimization of highly efficient transition metal-main group bifunctional catalysts in various catalytic applications. The bimetallic catalysts display remarkably enhanced activity compared to the analogous single metal centers. In this talk, I will detail the roles of the main group support in substrate binding, activation of strong bonds (C−F and C−H), and catalysis.