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Understanding the interface between soluble metal complexes and supported metal particles is important in order to reveal reaction mechanisms in a new generation of highly active homogeneous transition metal catalysts. In this study, we show that, in the case of palladium forming on a carbon (Pd/C) catalyst from a soluble Pd(0) complex Pd2dba3, the nature of deposited particles on a carbon surface turns out to be much richer than previously assumed, even if a very simple experimental procedure is utilized without the use of additional reagents and procedures. In the process of obtaining a heterogeneous Pd/C catalyst, highly active “hidden” metal centers are formed on the carbon surface, which are leached out by the solvent and demonstrate diverse reactivity in the solution phase. The results indicate that heterogeneous catalysts may naturally contain trace amounts of molecular monometallic centers of a different nature by easily transforming them to the homogeneous catalytic system. In line with a modern concept, a heterogenized homogeneous catalyst precursor was found to leach first, leaving metal nanoparticles mostly intact on the surface. In this study, we point out that the previously neglected soft leaching process contributes to high catalyst activity. The results we obtained demand for leaching to be reconsidered as a flexible tool for catalyst construction and for the rational design of highly active and selective homogeneous catalytic systems, starting from easily available heterogeneous catalyst precursors.