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Reversible-deactivation radical polymerization (RDRP) serves as a powerful tool nowadays for the preparations of unique linear and non-linear macromolecules. In this study, enhanced spin capturing polymerizations (ESCPs) of styrene (St) and <i>tert</i>-butyl acrylate (tBA) monomers were, respectively, conducted in the presence of difunctional (1Z,1′Z)-1,1′-(1,4-phenylene) bis (<i>N</i>-<i>tert</i>-butylmethanimine oxide) (PBBN) nitrone. Four-arm (PSt)₄ and (PtBA)₄ star macroinitiators (MIs) can be afforded. By correspondingly switching the second monomer (i.e., tBA and St), miktoarm star copolymers (μ-stars) of (PSt)₂-μ-(PtBA-<i>b</i>-PSt)₂ and (PtBA)₂-μ-(PSt-<i>b</i>-PtBA)₂) were thus obtained. We further conducted hydrolysis of the PtBA segments to PAA (i.e., poly(acrylic acid)) in μ-stars to afford amphiphilic μ-stars of (PSt)₂-μ-(PAA-<i>b</i>-PSt)₂ and (PAA)₂-μ-(PSt-<i>b</i>-PAA)₂. We investigated each polymerization step and characterized the obtained two sets of “sequence-isomeric” μ-stars by FT-IR, ¹H NMR, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA). Interestingly, we identified their physical property differences in the case of amphiphilic μ-stars by water contact angle (WCA) and atomic force microscopy (AFM) measurements. We thus proposed two microstructures caused by the difference of polymer chain sequences. Through this polymerization transformation (<i>Ŧ</i>) approach (i.e., ESCP-<i>Ŧ</i>-NMP), we demonstrated an interesting and facile strategy for the preparations of μ-stars with adjustable/switchable interior and exterior polymer structures toward the preparations of various nanomaterials.