In the reverse micelle systems formed by cyclohexane and non-ionic surfactants Pluronic L44, Pluronic L64, NP-7, AEO-7, Triton X-10 and Brij-58 respectively, nickel nitrate was added and then reduced with the introduction of hydrazine hydrate, and then coated with silica which was realized by the hydrolysis of TEOS. The products were collected by centrifugation and dried under air and then calcinated under nitrogen atmosphere and reduced by hydrogen flow. The as-synthesized products were characterized by TEM and XRD. The results showed that hollow spherical structure was obtained when Brij-58 was used and hollow tubular materials when Pluronic L44, Pluronic L64, NP-7, AEO-7 and Triton X-100 were used. The formation mechanism was also investigated. The reduction of p-nitrophenol with NaBH4 as model reaction was used to test the catalytic activity of hollow Ni@SiO2-Brij-58. It showed that the conversion rate of p-nitrophenol was 97.6% within 15 min.