A high internal phase emulsion (HIPE) method was used to produce adsorbents with an interconnected porous structure. HIPE was prepared using vinyl benzyl chloride (VBC), divinylbenzene (DVB), tert-butyl acrylate, and Span80 as the organic phase and water with K2S2O8 and CaCl2 as the water phase. The polymerization of the organic phase produced highly porous polymers called polyHIPE, carrying two functional groups. As a result of the template method, polyHIPEs have a low surface area. To overcome this drawback, polyHIPE was hyper-cross-linked through VBC to create meso-and micropores, resulting in a higher surface area. Then the polymer surface was tailored with carboxylic acid groups by simple hydrolysis of tert-butyl acrylate. The adsorption performances of the acidic functional hyper-cross linked polyHIPEs prepared for the various reaction times of 0, 15, and 60 min were compared for methylene blue. The hyper-cross-linked polyHIPEs showed an enhanced adsorption kinetics for methylene blue, and the 15 min hyper-cross-linking reaction increased the rate of methylene blue adsorption significantly. It was proven that the polyHIPE adsorbent can be reused by treating it with an aqueous acidic solution in ethanol.