Macroporous materials polymerized from high internal phase emulsions (PolyHIPEs) possess well-defined interconnected porous structures and tunable device shapes. This provides interesting property characteristics well-suited for a variety of applications. However, such materials also demonstrate poor mechanical performances, which limit their potential use. As will be demonstrated, this results from the high surfactant content required by PolyHIPEs. Herein, a new approach is introduced for designing a highly efficient polymeric surfactant, which generates interconnected pores in PolyHIPEs through designing an incompatible surfactant and skeleton material. The surfactant also possesses a hyperbranched topology, which combines the strong amphipathy of small molecular surfactants and the nanosphere structure of Pickering emulsifiers to provide an excellent colloidal stability to HIPEs. A hyperbranched polyethylene having pendant sodium sulfonate groups (HBPE-SO3Na) was thus designed and synthesized via chain walking copolymerization of ethylene and 2-trimethylsilyloxyethyl acrylate followed by sulfonation. Stable HIPEs of styrene/divinylbenzene and water at a weight ratio of 1 to 5 were obtained with using HBPE-SO3Na. The polymerization of HIPEs produced interconnected macroporous polystyrenes (PSs) at a substantially lower surfactant content, for example, 0.5 wt % HBPE-SO3Na. The compressive Young's moduli of PolyHIPEs reached 104-111 MPa with 0.5-2 wt % HBPE-SO3Na, which is the first reported case of a PS-based PolyHIPE achieving its theoretical modulus. The PolyHIPE was used to support Au nanoparticles and embed in a column for oxidation of dimethylphenylsilane. A complete conversion of dimethylphenylsilanol was achieved with low column back pressure in a 50 h continuous reaction with no degradation of PolyHIPE integrity and mechanical property.