Reversible-addition fragmentation chain transfer (RAFT) polymerization has been widely explored since its discovery due to its structural precision, versatility, and efficiency. However, the lack of tunability of the polymer backbone limits some applications. Herein, we synergistically combine RAFT and step-growth polymerization mechanisms, by employing a highly selective insertion process of a single monomer with a RAFT agent, to achieve RAFT step-growth polymerization. A unique feature of the RAFT step-growth polymers is that each backbone repeat unit bears a pendant RAFT agent, which can subsequently graft side chains in a second polymerization step and afford molecular brush polymers. Enabled by cleavable backbone functionality, we demonstrate transformation of the resulting brushlike polymers into linear chains of uniform size upon a stimulus.