Strategic selection of glazing, its window-to-wall ratio, and wall thickness of building reduce the energy consumption in the built environment. This paper presents the experimental results of solar optical properties of five glasses: clear, tinted bronze, tinted green, bronze reflective, and polymer dispersed liquid crystal glasses. Laterite room models were modeled with four different thicknesses and four different glasses using Design Builder, and thermal simulation tests were carried out using Energy Plus. The energy savings and carbon emission mitigation prospective of a building’s glazing variety, window-to-wall ratio (WWR), and wall thickness were investigated. The results revealed that among the five window glasses studied, the polymer dispersed liquid crystal glazing window (PDLCGW) was found to be the most energy-efficient for low heat gain in laterite rooms. The laterite room with 0.23 m wall thickness and 40% PDLCGW WWR reduced 18.9% heat gain in comparison with the laterite room with 0.23 m wall thickness and 40% clear glass WWR. The laterite room of 0.23 m wall thickness with PDLCGW glazing of 40% WWR enhanced cooling cost savings up to USD 31.9 compared to the laterite room of 0.08 m wall thickness with 40% PDLCGW. The laterite room of 0.23 m wall thickness with PDLCGW glazing of 40% WWR also showed improved carbon mitigation of 516 kg of CO2/year compared to the 0.23 m wall thickness laterite room of 40% WWR with clear glass glazing. The results also showed that the laterite room with 0.23 m wall thickness and 100% clear glass WWR increased heat gain by 28.2% in comparison with the laterite room with 0.23 m wall thickness and 20% clear glass WWR. The results of this article are essential for the strategic design of buildings for energy saving and emission reduction.