Abstract: The dark-yellow clear block TiO2-SiO2 complex material was prepared with two-step sol-gel technique. Controlling the hydrolysis speed, the tetrabutyl titanate (TBOT) and n-Ethyl silicate (TEOS) were hydrolyzed simultaneously and the sol produced was dried to form gel at 60°C. Then, the gel was dried by supercritical drying method using alcohol as solvent and annealed at different temperatures. The morphology and structure of TiO2-SiO2 complex material were confirmed by means of TEM, XRD and FT-IR. The results showed that after annealing the nano-TiO2 powder grains of anatase structure were uniformly dispersed in amorphous-SiO2 matrix and there was a Ti-O-Si bond between TiO2 grains and SiO2 matrix. In the photocatalytic degradation the TiO2-SiO2 complex material presents better catalytic property and nearly 86% Rhodamine B is degraded within 1 hour. This TiO2-SiO2 complex material is easier to separate from solution by filtration or sedimentation and it is expected to be used widely in waste-water treatment.