A straightforward strategy involving a RAFT process and ring-opening polymerization was used to construct symmetric reduction-responsive amphiphilic A(2m)B(2n)C(2) (m≈n≈ 3) starlike terpolymers with precise microstructure, which could be efficiently converted into thiol-functionalized telechelic stars, degraded A(m)B(n)C miktoarm stars and comblike-linear multiblock copolymers via postmodification.