Among homopolypeptides, polyproline is unique due to its conformational flexibility between right-handed PPI and left-handed PPII helices. Herein, we designed a propargyloxy-functionalized proline-NCA monomer, so that the ring-opening polymerization (ROP) of the former provides a reactive propargyl group in each repeating unit to enable postpolymerization modifications. A close match between the feed ratio and degree of polymerization estimated using 1 H NMR along with a low dispersity (Đ) suggests that the ROP was executed in a controlled manner. We then used azide-yne click chemistry to prepare polyproline chains that had been triethyleneoxy (TEG)-functionalized (periodically grafted). Later, functionalized polyprolines were compared with native polyprolines in terms of thermoresponsive behavior using turbidimetric analysis, circular dichroism (CD), and variable temperature NMR (VT NMR) spectroscopy. Despite sharing similar polyproline backbones, these two polymers differ significantly in their thermoresponsive behavior. VT NMR and CD studies revealed that water-soluble TEG residues in combination with enhanced conformational stability of the functionalized polyproline could be the reason behind the different thermoresponsiveness between these two polymers.