Porous polymer membranes with highly interconnected open-cellular structure and high toughness are crucial for various application fields. Polymerized high internal phase emulsions (polyHIPEs), which usually exist as monoliths, possess the advantages of high porosity and good connectivity. However, it is difficult to prepare membranes due to brittleness and easy pulverization. Copolymerizing acrylate soft monomers can effectively improve the toughness of polyHIPEs, but it is easy to cause emulsion instability and pore collapse. In this paper, stable HIPEs with a high content of butyl acrylate (41.7 mol% to 75 mol% based on monomers) can be obtained by using a composite emulsifier (30 wt.% based on monomers) consisting of Span80/DDBSS (9/2 in molar ratio) and adding 0.12 mol·L-1 CaCl2 according to aqueous phase concentration. On this basis, polyHIPE membranes with high open-cellular extent and high toughness are firstly prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. The addition of the RAFT agent significantly improves the mechanical properties of polyHIPE membranes without affecting open-cellular structure. The toughness of polyHIPE membranes prepared by RAFT polymerization is significantly enhanced compared with conventional free radical polymerization. When the molar ratio of butyl acrylate/styrene/divinylbenzene is 7/4/1, the polyHIPE membrane prepared by RAFT polymerization presents plastic deformation during the tensile test. The toughness modulus reaches 93.04 ± 12.28 kJ·m-3 while the open-cellular extent reaches 92.35%, and it also has excellent thermal stability.