Using host-guest interactions between β-cyclodextrin-modified branched polyethyleneimine and ferrocene-terminated poly-L-lactide, the formation, assembly and jamming of polyethyleneimine surfactants (PEISs) at the liquid-liquid interface is presented. With PEIS, reconfigurable liquids with electrochemical redox responsiveness can be constructed. In conjunction with microfluidic methods, continuous, selective diffusion and purification of ionic species can be achieved in all-liquid constructs.