Carbon microspheres with controllable porous structure were directly fabricated from waste Camellia oleifera shells through hydrothermal carbonization combined with physical activation or KOH chemical activation technique. The morphology, textural property, and compositional and structural information of as-prepared carbon materials were well characterized. The as-prepared aromatic carbon microspheres exhibit a perfectly spherical structure under carefully controlled hydrothermal carbonization conditions, whereas the as-prepared porous carbon microspheres feature a large surface area and a controllable porous structure. Subsequently, the porous carbon microspheres obtained by KOH chemical activation were successfully applied to the quick removal of phenolic organic pollutants from water. In addition, this paper further elucidated the mechanisms underlying the fabrication of spherical microstructure and controllable porous structure through hydrothermal carbonization of waste Camellia oleifera shells and pore-fabricating technique.