Single-pane windows still account for a large percentage of the US building energy consumption. In this paper, we introduced a new solution incorporating the photothermal effect of metallic nanoparticles (Fe3O4@Cu2-xS) into glazing structures to utilize solar infrared and then enhance the window's thermal performance in winter. Such spectrally selective characteristics of the designed photothermal films were obtained from lab measurements and then integrated into a thermodynamic analytical model. Subsequently, we examined the thermal and optical behaviors of the photothermal single-pane window and compared its overall energy performance with the conventional low-e coated single-pane window, in which typical window properties, dimensions, winter boundary conditions, and solar irradiance were adopted. The numerical analysis results demonstrated that the photothermal window systems could yield 20.4% energy savings relative to the conventional low-e coated windows. This research paves an underlying thermodynamic mechanism for understanding such a nanoscale phenomenon at the architectural scale. From the implementation perspective, the designed photothermal film can be added into the existing single-pane windows for energy-efficient retrofitting purposes.