We here show that a dendritic molecule combined with ligand merit confers supported platinum nanoclusters (PtNCs) with unprecedented catalytic performance. Branched polyethylenimine (PEI, Mn = 2000 D) patched on a porous bead is modified with 2-(diphenylphosphino)benzaldehyde (dppb) before being used to mediate a platinum nanoparticle/nanocluster (Pt0). The catalytic activity of Pt0 toward the reduction of 4-nitrophenol (4-NP) is evaluated from the parameter of Pt-normalized rate constant (kc). Optimization of the dppb level along with transformation of the PEI hydrogens into diol or trimethylammonium groups imparts supported Pt0 unprecedented activity (kc = 19.2 L mmol-1 s-1 and turnover frequency (TOF) = 1041 h-1). The supported Pt0 at an extremely low dosage of 0.1 ppm promotes 98% conversion of 4-NP within minutes and is well recyclable. The striking catalytic activity is attributed to the combination of orthogonal ligand properties such as weak ligand nature, catalyst-activating ability, excellent substrate affinity, and effect on PtNC-size mediation of the ligand.