Supported Ni catalysts on three mesoporous SiO supports (i.e., SBA-15, MCM-41, and HMS) were prepared using a solid-state reaction between Ni(NO) and organic template-occluded mesoporous SiO. For comparison, supported Ni catalysts on mesoporous SiO synthesized by the conventional impregnation method were also included. The catalysts were characterized by scanning electron microscopy, X-ray diffraction, UV-vis diffuse reflectance spectroscopy, N adsorption, X-ray photoelectron spectroscopy, H temperature-programmed reduction, transmission electron microscopy, and transmission electron microscopy-energy-dispersive X-ray. The catalytic properties of the catalysts were evaluated using gas-phase catalytic hydrodechlorination of 1,2-dichloroethane. The results showed that upon grinding Ni(NO) with template-occluded mesoporous SiO, strong coordination between Ni and dodecylamine was identified in the Ni(NO)-HMS system. Additionally, the results of H temperature-programmed reduction revealed that NiO in calcined NiO/HMS was reduced at higher temperature than those in calcined NiO/SBA-15 and NiO/MCM-41, reflecting the presence of a strong interaction between NiO and mesoporous SiO in NiO/HMS. Consistently, the average particle sizes of metallic Ni were found to be 2.7, 3.4, and 9.6 nm in H-reduced Ni/HMS, Ni/SBA-15, and Ni/MCM-41, respectively, indicative of a much higher Ni dispersion in Ni/HMS. For the catalytic hydrodechlorination of 1,2-dichloroethane, Ni/MCM-41 synthesized by the solid-state reaction method exhibited a catalytic activity similar to that prepared by the impregnation method, while higher catalytic activities were observed on Ni/HMS and Ni/SBA-15 than on their counterparts prepared by the impregnation method. Furthermore, a higher conversion was identified on Ni/HMS than on Ni/SBA-15 and Ni/MCM-41, highlighting the importance of template type for the preparation of highly dispersed metal catalysts on mesoporous SiO.