Carbon aerogel (CA), derived from phenolic (resorcinol and formaldehyde) resin, has being regarded as a promising porous adsorbent for water purification. In this study, we provided an effective strategy for preparing CA with a hierarchical porous microstructure. Acetic acid was introduced as an additive in the precursor solution to modify the microstructure of the xerogel, followed by KOH activation to further transform it into a hierarchical porous structure. The specific surface area of the hierarchical porous CA reached up to 1205.44 m2/g with a total pore volume exceeding 1.60 cm3/g. Consequently, the CA demonstrated an excellent adsorption rate, reaching adsorption equilibrium in approximately 240 min and exhibited a remarkable maximum dye adsorption capacity of 1.25 times its own mass. Furthermore, the adsorption processes of the CA for dye adhered to the second‐order kinetic model and the Langmuir isotherm model. This study provided an effective approach to preparing hierarchical porous CA for efficient adsorption of organic pollutants for water purification.