This study investigates the grafting of poly-sodium styrene sulfonate (pNaSS) from trichlorosilane/10-undecen-1-yl 2-bromo-2-methylpropionate functionalized Si and Ti substrates by atom transfer radical polymerization (ATRP). The composition, molecular structure, thickness, and topography of the grafted pNaSS films were characterized with x-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), variable angle spectroscopic ellipsometry (VASE), and atomic force microscopy (AFM), respectively. XPS and ToF-SIMS results were consistent with the successful grafting of a thick and uniform pNaSS film on both substrates. VASE and AFM scratch tests showed the films were between 25 and 49 nm thick on Si, and between 13 and 35 nm thick on Ti. AFM determined root-mean-square roughness values were $2 nm on both Si and Ti substrates. Therefore, ATRP grafting is capable of producing relatively smooth, thick, and chemically homogeneous pNaSS films on Si and Ti substrates. These films will be used in subsequent studies to test the hypothesis that pNaSS-grafted Ti implants preferentially adsorb certain plasma proteins in an orientation and conformation that modulates the foreign body response and promotes formation of new bone.