Abstract: Self-assembly is generally a spontaneous organization driven by non-covalent interactions including hydrogen bonds, Van der Waals forces and electrostatic force, leading to well-controlled nanostructures and materials. Among the building blocks for self-assembly, diblock copolymers with two segments containing different chemical groups could be applied to prepare multiple responsive materials, which have been widely used in a variety of fields covering adsorbents, catalysts, coatings, biosciences and materials science due to their microscopic dimensions and their responsiveness to specific stimuli. For example, by combining segments with pH-and temperature-responses, it is possible to form macromolecules that response to both temperature and pH. In this paper, amphiphilic block copolymer PAA-b-PMAEFc was obtained by hydrolysis of block copolymer PtBA-b-PMAEFc, which was synthesized by the atom transfer radical polymerization (ATRP) with t-butyl acrylate and 2-(methacryloyloxy) ethyl ferrocene-carboxylate as monomers and ethyl-2-bromoisobutyrate as ATRP agent. Proton nuclear magnetic resonance spectroscopy (¹H-NMR) and gel permeation chromatograph (GPC) were used to characterize the chemical structure, molecular weight and molecular weight distribution. The critical micelle concentration (CMC) of the polymer was determined by fluorescence spectrophotometer. The self-assembly behaviors and structures of PAA-b-PMAEFc were investigated by DLS and TEM. The results showed that the proportion of the amphiphilic block copolymer PAA-b-PMAEFc had a significant effect on the assembly in aqueous solution. Vesicles and spherical aggregates form when the mass ratio of the hydrophilic and hydrophobic segments was high, while rod-like structure appeared when the segments mass ratio decreased.