Ni-rich Ni/SiO2 composite aerogels in which weight percentage of Ni could reach 60% werefirstly prepared by sol-gel process of Ni-containing tetraethyl orthosilicate (NiTEOS). The influenceof H2O, catalyst, solvent and compostcomposition of Ni-containing tetraethyl orthosilicate on the sol-gelprocess was discussed. The specific sufrace areas of Ni/SiO2 composite aerogels are in the rangeof 420~650m2/g.