To enhance the catalytic activity of gold nanoparticles (AuNPs) for the hydrogenation of nitro-aromatic chemicals, Pt was introduced into AuNPs to form “bare” PtAu alloy NPs using a physical approach, pulsed laser ablation in liquid (PLAL), on single metal-mixture targets. These PLAL-NPs are deemed to favor catalysis due to the absence of any surfactant molecules on their unique “bare and clean” surface. The PLAL-NPs were facilely assembled onto CeO₂ nanotubes (NTs) by simply mixing them without conducting any surface functionalization, representing another advantage of these NPs. Their catalytic activity was assessed in 4-nitrophenol (4-NP) hydrogenation. The reaction catalyzed by alloy-NP/CeO₂-NT catalysts demonstrates a remarkably higher reaction rate in comparison with that catalyzed by pure Au and Pt NPs, and other similar Au and Pt containing catalysts reported recently. A “volcano-like” catalytic activity dependence of the alloy NPs on their chemical composition suggests a strong synergistic effect between Au and Pt in the 4-NP reduction, far beyond the simple sum of their individual contributions. It leads to the significantly enhanced catalytic activity of Pt₃₀Au₇₀ and Pt₅₀Au₅₀ alloy NPs, outperforming not only each single constituent, but also their physical mixtures and most recently reported AuNP based nanocatalysts. The favorable d-band center shift of Pt after alloying, and co-operative actions between Pt clusters and nearby Au (or mixed PtAu) sites were proposed as possible mechanisms to explain such a strong synergistic effect on catalysis.