Abstract Developing large pore volume mesoporous metal‐organic frameworks (MOFs) is a reliable strategy for adsorbing high‐concentration benzene in the event of accidental leakage. Herein, a novel mesoporous Al‐based MOF, named ZJU‐928(Al), is synthesized using biphenyl‐3,4′,5‐tricarboxylic acid ligands and low toxic AlO 6 cluster. It has larger pore volume (1.05 cm 3 g −1 ), order hexagonal channel (32.10 Å), and higher specific surface area (2344 m 2 g −1 ). As relative pressure up to 0.10, benzene adsorption of ZJU‐928(Al) rises to 9.99 mmol g −1 , exhibiting an excellent saturation benzene adsorption of 11.37 mmol g −1 at 298 K. The isosteric heat of adsorption for benzene on ZJU‐928(Al) is only 24.52 kJ mol −1 at near‐zero loading, lower than that of most reported MOFs, allowing for lower energy consumption during ZJU‐928(Al) regeneration. ZJU‐928(Al) has excellent cyclical benzene adsorption‐desorption performance, and highest benzene diffusivity coefficient (2.65 × 10 −5 cm 2 s −1 ). Simulation shows that the excellent saturation benzene adsorption performance of ZJU‐928(Al) can be attributed to the larger pore volume accommodating more benzene molecules. Consequently, this research synthesizes a novel mesoporous Al‐based MOF with excellent saturation benzene adsorption, highlighting the potential of MOFs for high‐concentration toxic gas adsorption.