Crystallized anatase TiO2 microflowers with high surface area are synthesized by a simple template-free solvothermal method using N,N-dimethylformamide (DMF). Titanium sources undergo well-organized assembly in DMF to form flower-shaped TiO2 particles. After the calcination, the anatase frameworks are highly crystallized, and the surface area is increased up to 256 m2 x g(-1). The calcined TiO2 microflowers show superior photocatalytic performance over the commercially available TiO2 product (P25) in the degradation of methylene blue.