The correlation of photo‐catalyst morphological structure and catalytic performance is one of the biggest challenges in the photo‐catalysis field. This work address a thorough investigation on the relationship between catalyst morphological structure and catalytic performance for the degradation of Direct Blue under ultraviolet light illumination. Four anatase Titanium dioxide catalysts with a slice‐, bipyramids‐, daisy‐, and sphere‐like morphologies were prepared by hydrothermal methods and well characterized by a serial of characterization techniques. By evaluating the photo‐catalytic performance over four kinds of TiO2 with different morphologies, the structure‐performance relationship of degradation of Direct Blue could be well illustrated. The degradation efficiency of TiO2 catalyst did much depend on the structure of catalyst shapes. The daisy‐like TiO2 catalyst exhibited the most excellent catalytic performance for the degradation of DB, which was attributed to the lowest band gap energy evidenced by UV‐vis spectrum.