Nanoparticle‐cored (NP‐cored) ferrocenyl dendrimers are precise multifunctional supramolecular nanomaterials owing to their active central and terminal groups and high (1→3) branching connectivity. For instance, catalysis in the interior of the metallodendrimer remains intriguing, especially because sulfur ligands have the reputation to inhibit catalytic reactions on surfaces. A nonaferrocenyl thiol dendron, 1, was utilized to prepare PdNP‐cored metallodendrimers (FcD‐PdNPs) 2, which were characterized by 1H, 13C NMR and FTIR spectroscopy, elemental analysis, and TEM. The ratio of precursor complex [PdCl2(MeCN)2] to dendron 1 was demonstrated to play a key role in the effectiveness of 2 as catalyst in Suzuki–Miyaura and styrene hydrogenation reactions, and a ratio of 5:1 optimized intradendritic catalytic activity for styrene hydrogenation at room temp. and 1 atm H2.