Polymer brushes are promising many applications as smart materials and biocompatible surfaces. Surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization is one of the most effective techniques for synthesis of well-defined polymer brushes. Herein, a biocompatible, uniform and stable poly(N-acryloylmorpholine)-silicon hybrid system was achieved using surface-initiated RAFT polymerization. Evidence of a well-controlled surface-initiated RAFT polymerization was confirmed by a linear increase of number average molecular weight (Mn) with overall monomer conversions. Water contact angle, ellipsometry, X-ray photoelectron spectroscopy and atomic force microscopy verified the presence of poly(N-acryloylmorpholine) (poly(NAM)) on silicon wafers. The grafting density (σ) and the average distance between grafting points (D) were estimated to be 0.58 chains/nm2 and 1.5 nm, respectively. The ratio of D value to radius of gyration (Rg) value is smaller than 1 (D/2Rg < 1), which corresponds to the brush regime of all grafted poly(NAM) films.