Novel polyelectrolytes consisting of hydrophobic polyolefin backbones and charged oligopeptide grafts have been synthesized and characterized. Oligopeptide-containing monomers were prepared by solid-phase peptide synthesis (SPPS) and then polymerized by ring-opening metathesis polymerization (ROMP). Copolymerization of the peptide-functionalized monomers with charge neutral cyclic olefins (i.e., poly(ethylene glycol)substituted) gave polymers with varying charge density. These graft copolymers were characterized by nuclear magnetic resonance (NMR) spectroscopy, organic and aqueous gel permeation chromatography (GPC), and light scattering. Light scattering indicated that the oligopeptide-functionalized polyolefins could be tailored to form extended, pearl-like, or multimolecular structures, depending on the composition and density of the grafts.