Cationic surfactant, quaternary ammonium salt of lignin, was synthesis from the lignin and trimethylamine though Mannich Reaction. Then quaternary ammonium salt of lignin was used as a novel template to prepare nanostructural silica from TEOS by sol-gel templating method. After removing the template at 580°C, nanostructural silica were obtained. The results of SEM and TEM show that there were two kinds of the silica after calcined. One is 3-dimetional macroporous silica, with the pore size of 100-200 nm. The other kind of silica is nanoparticle: the particle sizes range from 20 to 200nm and the specific surface area is 387.6 m2•g-1.