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Increasing contamination risk from oil/organic liquid leakage creates strong demand for the development of absorbents with excellent hydrophobicity and absorption capacity. Herein, bagasse was carbonized to form porous char with a special structure of array-style and vertically perforated channels, and then the activation process enlarged the pore volume of the char. With the cooperation of low-surface-energy polydimethylsiloxane and diatomaceous earth particles, the modified activated carbon aerogel (MACA) was fabricated by modifying the surface coating and mastoid structure on the bagasse char. Moreover, the MACA demonstrates high porosity oil-water separation, hydrophobicity, and considerable absorption capacity (4.06–12.31 <i>g</i>/<i>g</i>) for gasoline and various organic solvents. This work converts agricultural waste into an efficient porous adsorbent, offering a scalable and commercially feasible solution to solving the leakages of oil/organic solvents.