Pharmaceutical and Personal Care Products (PPCPs) are emerging contaminants, which can affect water quality and potentially impact drinking water supplies, ecosystems and human health. A novel and unique structure, an octahedral bipyramid skeleton, assembled by three pieces of carbon self-doped TiO2 flakes with exposed {001} facets was explored for the first time to mineralize ciprofloxacin, one of PPCPs. The results demonstrated that the obtained C-doped TiO2 flakes presented higher visible-light photocatalytic activity in comparison with the reported C-doped TiO2 sheets with exposed {001} facets, which can be ascribed to the narrower band gap, the higher percentage of the exposed {001} facts, the larger specific surface area, and the unique octahedral bipyramid skeleton structure.