tThe scrupulous design of hierarchical structure and highly active crystal facets exposure is essential forthe creation of photocatalytic system. However, it is still a big challenge for scrupulous design of TiO2architectures. In this paper, bird’s nest-like anatase TiO2microstructure with exposed highly active (001)surface has been successfully synthesized by a facile one-step solvothermal method. Methylene blue(MB) is chosen as a model pollutant to evaluate photocatalytic activity of as-obtained TiO2samples. Theresults show that the photocatalytic activity of the bird’s nest-like sample is more excellent than P25 inthe degradation of MB due to high specific surface area and highly active (001) crystal facets exposurewhen tested under simulated solar light. Besides, it can be readily separated from the photocatalyticsystem by sedimentation after photocatalytic reaction, which is a significant advantage against conven-tional powder photocatalyst. The bird’s nest-like microspheres with novel structure may have potentialapplication in photocatalysis and other fields.