This paper describes a methodology for preparing uniform, nanothin polymer films for the study of biomolecule adsorption by surface plasmon resonance spectroscopy (SPR). The methodology combines molecular self-assembly of alkanethiols on gold with surface-confined atom transfer radical polymerization (ATRP). Poly(2-vinylpyridine) was chosen to demonstrate the methodology, and growth kinetics were studied by ex situ ellipsometry. Atomic force microscopy (AFM) indicated that the polymer films were uniform With RMS roughness of similar to0.5 nm. Subsequent SPR measurements were done to determine thermodynamic adsorption properties (DeltaG, DeltaH, and DeltaS) between fibronectin adhesion-promoting peptide and the surface-confined poly(2-vinylpyridine) at 15, 20, and 25degreesC. The flexibility in synthesis conditions and the opportunities for manipulating film thicknesses and graft densities that ATRP provides to grow polymer films from gold surfaces holds advantages over conventional spin-coating and grafting to approaches in the design of model polymer films for biomolecule adsorption Studies. These advantages are described.