The aim of the present study was to investigate the thermal performance of window systems using full-scale measurements and simulation tools. A chamber was installed on the balcony of an apartment to control the temperatures which can create condensation on the interior surfaces of window systems. The condensation process on the window was carefully scrutinized when outdoor and indoor temperature and indoor relative humidity ranged from −15 °C to −20 °C, 23 °C to 24 °C, and 50% to 65%, respectively. The results of these investigations were analyzed to determine how the moisture is influenced by changing temperatures. It appears that the glass-edge was highly susceptible to the temperature variations and the lowest temperature on the glass edge was caused by the heat transfer through the spacer, between the two glass panels of the window. The results from the simulation used in this study confirm that the thermal performance of window systems can be improved the use of super insulated or thermally broken spacers. If the values of the indoor humidity and temperature are given, then the outdoor temperature when condensation forms can be obtained by using Temperature Difference Ratio (TDR). This methodology can be employed to predict the possible occurrence of condensation.