A gold nanoparticle (AuNP)-based colorimetric method was developed for the molecular weight (MW) determination of polyethylene glycol (PEG), a commonly used hydrophilic polymer. Addition of a salt solution to PEG-coated AuNP solutions helps in screening the electrostatic repulsion between nanoparticles and generating a color change of the solutions from wine red to blue in 10 min in accordance with the MW of PEG, which illustrates the different stability degrees (SDs) of the AuNPs. The SDs are calculated by the absorbance ratios of the stable to the aggregated AuNPs in the solution. The root mean square end-to-end length (〈h2〉1/2) of PEG molecules shows a linear fit to the SDs of the PEG-coated AuNPs in a range of 1.938 ± 0.156 to 10.151 ± 0.176 nm. According to the Derjaguin-Landau-Verwey-Overbeek theory, the reason for this linear relationship is that the thickness of the PEG adlayer is roughly equivalent to the 〈h2〉1/2 of the PEG molecules in solution, which determines the SDs of the AuNPs. Subsequently, the MW of the PEG can be obtained from its 〈h2〉1/2 using a mathematical relationship between 〈h2〉1/2 and MW of PEG molecule. Applying this approach, we determined the 〈h2〉1/2 and the MW of four PEG samples according to their absorbance values from the ordinary ultraviolet-visible spectrophotometric measurements. Therefore, the MW of PEG can be distinguished straightforwardly by visual inspection and determined by spectrophotometry. This novel approach is simple, rapid, and sensitive.