Different generations of poly(propylene imine) (G _n -PPI) terminated with N-containing 15-membered triolefinic macrocycle (G _n M) ( n = 2, 3, 4, 5) were prepared. The bimetallic nanoparticle catalysts G _n M-(Pt _x /Pd _{10− x} ) ( x = 0, 3, 5, 7, 10) were prepared by the synchronous ligand-exchange reaction between G _n M and the complexes of Pt(PPh ₃ ) ₄ and Pd(PPh ₃ ) ₄ . The structure and catalytic properties of G _n M-(Pt _x /Pd _{10− x} ) were characterized via Fourier transform infrared spectroscopy, ¹ H nuclear magnetic resonance spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, energy-dispersive spectroscopy and inductively coupled plasma atomic emission spectroscopy. The novel bimetallic Pd–Pt nanoparticle catalysts stabilized by dendrimers (DSNs) present higher catalytic activities for the hydrogenation of dimeric acid (DA) than that of nitrile butadiene rubber (NBR). It can be concluded that bimetallic Pd–Pt DSNs possess alloying and synergistic electronic effects on account of the hydrogenation degree (HD) of DA and NBR. Furthermore, the HD of DA and NBR shows a remarkable decrease with the incremental generations ( n ) of G _n M-(Pt ₃ /Pd ₇ ) ( n = 2, 3, 4, 5).