This research investigates the energy efficiency of a novel double-glazing system incorporating solid–solid phase change materials (SSPCMs), which offer significant advantages over traditional liquid–solid phase change materials. The primary objective of this study is to develop a 3D numerical model using the finite volume method, which will be followed by a parametric study under real climatic boundary conditions. A proposed double-glazing setup featuring a 2 mm layer of SSPCM applied on the inner glass pane within the air gap is modeled and analyzed. The simulations consider various transient temperatures and ranges of the SSPCM to evaluate the energy performance of the system under different weather conditions of Miami, FL during the coldest and hottest days of the year, both in sunny and cloudy conditions. The results demonstrate a notable improvement in energy performance compared to standard double-glazing windows (DGWs), with the most efficient SSPCM configuration exhibiting a phase transition temperature and range of 25 °C and 1 °C, respectively. This configuration achieved energy savings of 24%, 26%, and 23% during summer sunny, winter sunny, and winter cloudy days, respectively, relative to DGWs during cooling and heating degree hours. However, a 3% energy loss was observed during summer cloudy days. Overall, the findings of this study have shown the potential for energy savings by incorporating SSPCM with suitable thermophysical properties into double-glazing systems.