Nanomaterials have been widely used in environmental cleanup, especially in the removal of pollutants, because of their fairly high specific surface area, surface energy and catalytic activity. Recently, there is a growing interest in 3D micro/nano material constructed with nanosized building blocks hierarchically, for they hold the advantages of not only microstructure but also nanostructure. Chlorinated aromatics are ubiquitous and highly harmful for human and eco-environment. However, the available disposal technologies for this type of pollutants have the drawbacks such as time-consumption, the release of secondary pollutants and high cost. Therefore, it is significantly required to develop an efficient, environmentally benign, and economic technology for detoxifying chlorinated aromatics. Application of novel micro/nano material in the degradation of chlorinated aromatics might provide a promise in this field. In this study, a series of self-assembled three dimensional (3D) hierarchical micro/nano materials were synthesized by the polyol-mediated process, for degradation of Hexachlorobenzene (HCB) as a model compound of toxic chlorinated benzene. The degradation activity of the synthesized materials and degradation kinetics of HCB were evaluated, and the degradation products were identified to understand the degradation process. The main contents were as follows.