Gold nanoparticles (AuNPs) have significant potential as biosensors and drug delivery vehicles, as well as imaging and thermotherapy agents. Thiol-containing polyethylene glycol (PEG), hereafter denoted as thiol-PEG, is widely used as a macromolecular ligand for modifying AuNPs and stabilizing them under various environments. In this work, a series of thiol-PEG-modified AuNPs (PEGylated AuNPs) with different PEG molecular weights (M-w) were synthesized. The saturated capping density, charge-screening ability, and stability of the PEGylated AuNPs were then examined. The results showed that high-M-w PEG stabilized the AuNPs and screened the surface charge better than low-M-w PEG, but the latter showed higher saturated capping density. More importantly, PEG exhibited the maximum coagulation concentration (MCC) and critical stabilization concentration (CSC) in the stabilizing process of the AuNPs. Thiol-PEG acted as an AuNP stabilizer only when its concentration was higher than the CSC. Otherwise, thiol-PEG accelerated AuNPs aggregation, which reached the peak level at the MCC. These results were significant in recognizing the influence of thiol-PEG on the stability of AuNPs. (C) 2013 Elsevier Inc. All rights reserved.