An amphiphilic heteroeight-shaped polymer cyclic-[poly(ethylene oxide)-b-polystyrene](2) ([c-(PEO-b-PS)](2)) composed of hydrophilic PEO and hydrophobic PS blocks was synthesized by combination of "click" chemistry with anionic ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP) mechanisms. According to "core-first" strategy, the A(2)B(2) star-shaped precursor (PEO-alkyne)(2)-(PS-N-3)(2) was obtained by successive ROP of EO monomer, ATRP of St monomer, and modification of functional groups. Under high dilution condition, the intramolecular cyclization of (PEO-alkyne)(2)-(PS-N-3)(2) by "click" chemistry produced the amphiphilic heteroeight-shaped polymer [c-(PEO-b-PS)](2). The target copolymers and intermediates were well characterized by GPC, MALDI-TOF MS, H-1 NMR, and FT-IR The self-assembly behavior of [c-(PEO-b-PS)](2) and its precursor of (PEO-alkyne)(2)-(PS-N-3)(2) were investigated and compared by transmission electron microscopy (TEM) and dynamic light scattering (DLS). In both cases, the spherical micelles were observed, however, the size of formed micelles increased from a star-shaped to a cyclic topology.