Herein, we reported a novel strategy to synthesize CuO@SiO2 nanocomposites under neutral conditions with the self-catalysis effect of APTES and CuBA(2) as proper precursor. No additional acid or alkali was required as catalyst during the entire process. On the other hand, the catalytic properties of CuO@SiO2 composites were evaluated by catalyzing the reduction of 4-nitrophenol using NaBH4 as the reducing agent. The results revealed that the products exhibit excellent catalytic property and cycling performance.