Polyprolines are attractive polymers because of their folding property into polyproline II (PPII) structure, their significance in protein/protein interactions, and their potential as new therapeutic targets. Silaproline (Sip) is an analogue of proline, which exhibits similar conformational properties. The presence of dimethylsilyl group confers to Sip a higher lipophilicity as well as an improved resistance to biodegradation. Enantiomerically pure Sip was available in gram quantities from resolution of the enantiomers by chiral high performance liquid chromatography. This study describes the first synthesis of Sip N‐carboxyanhydride (NCA) and shows preliminary results on comparison of polymerization of (l)Pro‐NCA and (d)Sip‐NCA to obtain homopolypeptides with PPII structure, polyproline, and polysilaproline polymers.