In order to well arrange active sites and avoid byproducts, the reasonable structured carrier nanocatalyst plays a crucial role in high catalytic performance, but still remains a challenge. Herein, the layered CuNi-Cu₂O/NiAlO_x nanosheets have been constructed through hydrothermal synthesis followed by calcination and H₂ reduction treatment process. The in-situ formed CuNi nanoalloys (NAs) and nano-Cu₂O were evenly distributed on the bilateral surface of layered NiAlO_x nanosheets. Based on the planar structure of nanosheet, the synergy between catalytic active CuNi NAs and photocatalytic active nano-Cu₂O endows CuNi-Cu₂O/NiAlO_x nanosheets with rapid conversion efficiency for catalyzing p-nitrophenol (p-NP, 14 mg·L^-1) to p-aminophenol (p-AP) in 32 s with the reaction rate constant k up to 0.1779 s^-1, and no obvious performance decay can be observed even over 27 cycles. Moreover, high concentration of p-NP at 10 and 20 g·L^-1 could be reduced to p-AP within 14 and 20 min, respectively. Such designed nanoalloy/bimetal-oxide heterostructure can provide a solution for rapid conversion of aminoaromatics from nitroaromatics wastewater even at a large concentration range.