In this paper, CuxOAu–ZnO nano-catalysts with different morphologies were synthesized by one-step replacement method. The nano-catalysts are characterized by scanning electron microscopy, energy-dispersive X-ray analysis, transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. These novel CuxOAu–ZnO nano-catalysts exhibit exceptionally high stability and superior 4-nitrophenol to 4-aminophenol hydrogenation ability. The relationship between catalytic performances and changes of composition were investigated, and the catalytic activity decreased in the following order: CuxO30Au35–ZnO > CuxO38Au35–ZnO > CuxO21Au45–ZnO. The influence of catalytic conditions for the performance of catalysts has also studied. For the CuxO30Au35–ZnO catalysts, the rate constant kapp could be up to 18.6 × 10−3 s−1, and the conversion of the 4-NP could still reach 98.66% after five cycles. The high activity of CuxO30Au35–ZnO may be attributed to the synergistic effect between Au and Cu element. The unique structure and high catalytic performance make CuxOAu–ZnO nano-catalysts for practical applications in 4-nitrophenol reduction. [ABSTRACT FROM AUTHOR]