Maintaining specific conformations of peptide ligands is crucial for improving the efficacy of biological interactions. Here, a one‐pot polymerization strategy for stabilizing the α‐helical conformation of peptides while simultaneously constructing multimeric ligands is presented. The new method, termed stapling polymerization, uses radical polymerization between acryloylated peptide side chains and vinylic monomers. Studies with model peptides indicate that i, i+7 crosslinking is effective for the helix stabilization, whereas i, i+4 crosslinking is not. The stapling polymerization results in the formation of peptide–polyacrylamide conjugates that include ≈3–16 peptides in a single conjugate. This stapling polymerization provides a simple but powerful methodology to fabricate multimeric α‐helices that can further be developed to modulate multivalent biomacromolecular interactions.