Carboxyl-modified block amino silicone polyether (MAn-BPEAS) was prepared using block amino silicone polyether (BPEAS) and Maleic anhydride (MAn). Chemical structure of MAn-BPEAS was characterized by IR. Then, MAn-BPEAS and BPEAS was emulsified with nonionic surfactant isomeric alcohol ethoxylates (XL) in order to achieve a translucent MAn-BPEAS and BPEAS microemulsion. The supramolecular emulsion (BPEAS/MAn-BPEAS) was got by mixing equal MAn-BPEAS and BPEAS microemulsion for electrostatic self-assembly under the guidance of the theory of self-assembly. The particle size of the emulsion micelles before and after the self-assembled was measured by Nano-particle surface potential analyzer. Then, the obtained supramolecular emulsion was applied on cotton fabric, and the fabric surface film morphologies observed by scanning electron microscopy(SEM). The applied performance of BPEAS、MAn-BPEAS and BPEAS/MAn-BPEAS emulsion was investigated.