We have investigated the thermally and photoinduced structural and chemical changes of a polyvinylpyrrolidone (PVP)-covered silver nanocube (AgNC) array on Au(111). The Langmuir–Blodgett (LB) method was utilized to fabricate the highly ordered array of the AgNC monolayer on Au(111). In the Raman spectra obtained at room temperature, sharp vibrational peaks were observed owing to the surface-enhanced Raman scattering (SERS) effect of AgNCs. When AgNCs were annealed, their corners became rounded, followed by their height decrease and lateral expansion. Simultaneously, PVP decomposed into nanocarbons, which were eliminated from the gap between AgNCs. Further annealing AgNCs/Au(111) resulted in obvious decreases in Raman signal intensity and AgNC height due to the sintering of AgNCs. We also confirmed the photochemical transformation of PVP to nanocarbons without the deformation of AgNCs when an intense laser was irradiated on the AgNC surface.