The colloidal stability of metal nanoparticles is tremendously dependent on the thermal behavior of polymer brushes. Neat polyethylene glycol (PEG) presents an unconventional upper critical solution temperature in ethanol, where phase segregation and crystallization coexist. This thermal behavior translated to a PEG brush has serious consequences on the colloidal stability in ethanol of gold nanoparticles (AuNPs) modified with PEG brushes upon cooling. We observed that AuNPs (13 nm diameter) stabilized with conventional linear PEG brushes (Mn = 6 and 11 kg mol-1) in ethanol suffer from reversible phase separation upon a temperature drop over the course of a few hours. However, the use of a polymer brush with cyclic topology as a stabilizer prevents sedimentation, ensuring the colloidal stability in ethanol at -25 °C for, at least, four months. We postulate that temperature-driven collapse of chain brushes promotes the interpenetration of linear chains, causing progressive AuNP sedimentation, a process that is unfavorable for cyclic polymer brushes whose topology prevents chain interpenetration. This study reinforces the notion about the importance of polymer topology on the colloidal stability of AuNPs.