We report a modular synthesis method toward precisely defined hydrogen-bonded polyacrylates. Various stickers are built into difunctional ATRP (Atom Transfer Radical Polymerization) initiators, which then allow the formation of polyacrylates with self-complementary stickers in the middle of the chain, the molar mass of which can be tuned within a large range (from 3 to 100 kg mol−1). These self-assembling polymers are characterized by FTIR and SANS in solution, showing that comb-shaped supramolecular polymers with a reversible backbone can be obtained.