In this article, we report the morphology modulation of gold nanoparticle (NP) arrays by polymer-assisted thermal treatment. Simultaneously, localized surface plasmon resonance (LSPR) UV–vis extinction (absorption plus scattering) of gold NP arrays was monitored and analyzed. First, through horizontal lifting, gold NP monolayers were transferred from a water/hexane interface to glass slides. After thin polymer films were spin-coated on the gold NP monolayers, thermal treatment was carried out, which results in apparent color changes in the obtained samples. The color changes could be attributed to the shift of the surface plasmon band (SPB), along with increasing gold NP size and interparticle distance. We found that different polymers show different effects on the modulation of gold NPs’ morphology, accompanied by different shifts of the SPB. Polymers with relatively lower glass transition temperatures (Tg), such as poly(methyl methacrylate), promoted gold NPs to merge into spheres, while polymers with r...