Hierarchically porous carbon monoliths (HPCMs) with both ordered hexagonal mesoporosity and three-dimensionally connected macroporosity were synthesized via a simple and time-saving hydrothermal process followed by a nanocasting pathway. These monoliths have high macropore volumes and specific surface areas, strong hydrophobicity, low densities and regular shapes. Importantly, these HPCMs showed excellent performance in cleaning/recycling spilled oils or organic solvents with high adsorption capacity, rate, stability, and reusability, and in adsorbing bilirubin with high adsorption capacity, blood compatibility and durability in plasma as well. The adsorption of oil was based on the dispersion interaction between gasoline molecules and the carbon basal planes of HPCMs, while the isotherm of bilirubin adsorption on the optimized HPCMs and the corresponding kinetic data were found better fitted by Langmuir adsorption model and pseudo-second-order kinetic model, respectively.