This article describes the first surface-initiated polymerization of isocyanide monomers onto various surfaces in a controlled manner. Brushes up to 200 nm could be easily obtained within 3 h of polymerization, and the polymer growth was studied as a function of reaction time, monomer concentration, and growth conditions, using atomic force microscopy (AFM) and ellipsometry. The monomers used in this study contain dipeptide (L,L-Ala-Ala) side groups; circular dichroism (CD) measurements, Fourier transform infrared spectroscopy (FTIR), and AFM confirmed that the well-defined helical conformation was retained in the polyisocyanide brushes with hydrogen bonds along the polymer chains.