To investigate the effect of various surfactant in the microstructure, using four surfactants as templates, Al doped titanium dioxide (Al-TiO2) powder with various properties were prepared by the same condition. And the materials microstuctures were characterized and analyzed. The results showed that carbon atomicity of hydrophobic groups in surfactant is negative to the crystallite size of Al-TiO2 powder and positive to the distorting stress. Moreover, the more the mass fraction that Al3 entered into TiO2 crystal lattice induced by the surfactant, the more the distorting stress produced by crystal lattice. Visible light degradation property of pyridine on the Al-TiO2 powder surface is mostly determined by the molecule structure of surfactant and thus the oxygen vacancy concentration induced by surfactant rather than the band gap width. In the controlling range of anion surfactant on the materials structure, SDS is stronger than that cation surfactant, but the ampholytic surfactant is poor.