Synthesis of novel amphiphilic supramolecular miktoarm star copolymers has been achieved through complementary molecular recognition and interactions between carboxy groups and amino groups. Polystyrenes carrying two and one carboxy groups at the middle of the polymer chain are used as precursors to react with poly(ethylene oxide) (PEO) end-capped with a primary amine functionality (-NH2) or a quaternary ammonium hydroxide functionality (-N+(CH2CH3)(3)OH-). The result suggests that the basicity of the amine plays a key role in the molecular recognition procedure. The efficiency of ionic bond formation can be enhanced from 40% up to 97% by using PEON+(CH2CH3)(OH-)-O-3 instead of PEO-NH2. The obtained supramolecular polymers can be dissociated in dilute acid solution at room temperature.