Using a facile approach,we successfully made large “defect-free” hyperbranched polystyrene (PSt) chains with uniform subchains between two branching points from the interchain “clicking” of a Seesaw-type linear macromonomer [azide～～～alkyne～～～azide] prepared by ATRP with a following conversion of two bromine-ends into two azide-ends,where～～～denotes a PSt chain with a molar mass in the range 1.65-31.0 kg/mol.