We report here a straightforward route to polymer peptide conjugates via the convenient synthesis of SG1-functionalized peptides able to initiate nitroxide-mediated polymerization (NMP). The NMP initiator SG1-functionalized peptide (SG1-GGGWIKVAV) was prepared by solid-phase peptide synthesis (SPPS) using an automated synthesizer, with a last step consisting of reaction between the carboxylic acid function of the MAMA-SG1 (BlocBuilder) alkoxyamine with the peptide terminal amine in the presence of benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBOP) as coupling agent. The resulting SG1-functionalized resin-attached peptide was used to perform the controlled NMP of styrene, leading after trifluoroacetic acid cleavage to the corresponding polystyrene-peptide conjugate. The latter was thoroughly characterized by UV spectrometry, gel permeation chromatography (GPC), H-1 NMR, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS).