Global demand for energy in the construction sector has increased drastically. A substantial portion of this energy belongs to fulfilling the heating, ventilation, and air-conditioning requirements of buildings, which are essential for maintaining the well-being of people. The development of zero-energy or environmentally friendly structures is required to attain a sustainable future. Strategic design of the building’s envelopes in green energy buildings can reduce air conditioning expenses. This article focuses on several insulation-integrated fly ash brick wall envelopes that have been designed to reduce CO2 emissions, reduce air conditioning expenses, and figure out payback times in warm-temperate and hot-arid regions. The degree-hour technique for heating and cooling, as well as unsteady heat transfer characteristics, are taken into consideration in this research. This is achieved by incorporating thirteen innovative insulation materials into fly ash bricks in three distinct configurations, (i.e., insulation layer near to the outer end of the fly ash block, on the middle of the fly ash block, and near to the inside end of the fly ash block). Experimental measurements were carried out to determine the thermo-physical characteristics of insulation materials. The analytical findings are confirmed through experimental validation. In hot-arid and composite climatic zones, placing an insulation layer (cloth-40/foam-60) near the outer end of the fly ash block resulted in the highest savings on air-conditioning costs of 0.89 $/m2 and 0.90 $/m2, respectively. They also achieved the highest carbon mitigation values at 17.2 and 16.8 kg/kWh. Insulation-integrated wall envelopes represent the pinnacle of energy efficiency in green building design, seamlessly combining advanced insulation materials with cutting-edge construction techniques to minimise energy consumption and maximise sustainability.