Hierarchically porous materials with multiple pore structures have the potential application in catalysis, separation or bioengineering. A concept was introduced to design and fabricate hierarchically porous hybrid materials (HPHMs) simultaneously containing mesopores and macropores. The proof-of-concept design was demonstrated by fabrication of several kinds of hybrid materials by adding degradable polycaprolactone (PCL) additive, which was simple and easy-operating. The specific surface areas of HPHMs prepared with polyhedral oligomeric vinylsilsesquioxanes (vinylPOSS) and 1,4-dithiothreitol (DTT) could reach 727 m(2)/g by adding 25% PCL additive, while the HPHMs were imperforate prior to degradation of PCL. The characterization further indicated that the macropores could be controlled by the amount of PCL additive. Moreover, the porous properties of HPHMs were influenced by the molecular weight of PCL. Other dithiols compounds were also successful in preparing HPHMs with high specific surface areas over 400 m2/g. Due to hydrophobic interaction and hydrogen bond interaction, the HPHM exhibited good adsorption ability for bisphenol A (BPA) in aqueous solution. Adsorption equilibrium could be achieved within 30 min, and the adsorption capacity was up to 157.4 mg/g. Meanwhile, the removal efficiency was found to be 95.37% for BPA.