Here, a new procedure and method are presented for the production of highly grafted polymer brushes. Thiol-terminated polyethylene oxide (PEO-SH) of molecular weight (M(w)) 20,000 (20k) is grafted to a gold surface from highly concentrated aqueous solutions of nonthiolated polyethylene oxide homopolymer. The M(w) and volume fraction of the homopolymer solution are varied in order to control the grafting density of the resulting PEO-SH brush. As a result, 20k M(w) PEO-SH brushes with grafting densities up to 0.3 chains/nm(2) are achieved, as determined by ellipsometry. Highly concentrated homopolymer solutions of volume fraction greater than approximately 12% and M(w) greater than approximately 938 produce near-ideal solvent conditions for the 20k M(w) PEO-SH chains; we have found that this facilitates the achievement of higher grafting densities of end-functionalized polymer brushes than would be possible from simple solutions. We propose this as a suitable method for applications where the grafting density of a brush surface must be accurately varied and controlled consistently. The effect of chemisorption time and cleaning procedure on the resulting brush grafting density are also explored.