Bifunctional catalysts offer unprecedented opportunities for new and improved reactivity and selectivity. The combination of a metal's d electrons and a pendant base or acid in the vicinity of an organometallic active site leads to rate accelerations of 1000 to 10 000 fold in the cases of alkyne hydration and alkene isomerization. The focus of this perspective is on work from our labs on bifunctional catalysts, catalytic intermediates, and related complexes. Particular attention is paid to the structures and properties related to catalyst performance.