The window-to-wall ratio (WWR) significantly affects the indoor thermal environment, causing changes in buildings’ energy demands. This research couples the “Envi-met” model and the “TRNSYS” model to predict the impact of the window-to-wall ratio on indoor cooling energy demands in south Hunan. With the coupled model, “Envi-met + TRNSYS”, fixed meteorological parameters around the exterior walls are replaced by varied data provided by Envi-met. This makes TRNSYS predictions more accurate. Six window-to-wall ratios are considered in this research, and in each scenario, the electricity demand for cooling is predicted using “Envi-met + TRNSYS”. Based on the classification of thermal perception in south Hunan, the TRNSYS predictions of the electricity demand start with 30 °C as the threshold of refrigeration. The analytical results reveal that in a 6-storey residential building with 24 households, in order to maintain the air temperature below 30 °C, the electricity required for cooling buildings with 0% WWR, 20% WWR, 40% WWR, 60% WWR, 80% WWR, and 100% WWR are respectively 0 KW·h, 19.6 KW·h, 133.7 KW·h, 273.1 KW·h, 374.5 KW·h, and 461.9 KW·h. This method considers the influence of microclimate on the exterior wall and improves the accuracy of TRNSYS in predicting the energy demand for indoor cooling.