A necessary step in advancing the use of polyethylene glycol (PEG) surface coatings in critical biotechnological applications such as cancer treatments is to provide direct and reliable nanoscale property characterization. Measurements for such characterization are currently provided by scanning probe methods, which are capable of assessing heterogeneity of both surface coverage and properties with nanoscale spatial resolution. In particular, atomic force microscopy (AFM) can be used to detect and quantify the heterogeneity of surface coverage, whereas atomic force spectroscopy can, be used to determine mechanical properties, thereby revealing possible heterogeneity of properties within coatings. In this work, AFM and force spectroscopy were used to characterize the morphology and mechanical properties of thiol-functionalized PEG surface coatings on flat gold substrates in aqueous PEG solution. Thiol-functionalized PEG offers a direct and simple method of attachment to gold substrates without intermediate anchoring layers and therefore can be exploited in developing PEG-functionalized gold nanoparticles. AFM was used to investigate the morphology of the PEG coatings as a function of molecular weight; the commonly observed coverage was in the form of sparse, brushlike islands. Similarly, force spectroscopy was utilized to study the mechanical properties of the PEG coatings in compression and tension as a function of molecular weight. A constitutive description of the mechanical properties of PEG brushes was achieved through a combinatorial analysis of the statistical responses acquired in both compression and tension tests. Such a statistical characterization provides a straightforward procedure to assess the nanoscale heterogeneity in the morphology and properties of PEG coverage.