Bio-butanol as a renewable energy can be produced through biomass fermentation. Among these, the adsorption-based technique is the most energy-efficient. However, the adsorption of small amounts of butanol from the aqueous phase remains a challenge. In this work, poly (methyl methacrylate)-based (PMMA) cryogel particles with tunable polarity and a super-macroporous structure were prepared by combining a simple dropping method and sulfolane freeze casting. The maximum adsorption capacities of the PMMA cryogel particles using the batch shaking and fixed-bed were 520.2 and 1442.2 mg/g, respectively. Adsorption rate constant of amphiphilic cryogel particles increased by approximately 9–40 times compared with PMMA cryogel particles. Adsorption capacity of the PMMA-based cryogel particles was maintained at 99 % of the initial adsorption capacity after 10 cycles. This study presented a strategy for the design of adsorbents with super-macroporous structures and hydrophilic modification to facilitate the adsorption of hydrophobic butanol from the aqueous phase system.