Energy conservation in buildings plays a vital role for sustainable development of societies and nations. Although, newer buildings in developing nations are being constructed using energy conservation approach, existing buildings have higher energy demand to meet the desired comfort. Excessive energy demand for cooling the built environment is a major problem over most of the arid climatic zones. The problem is predominant in all the top storied buildings which are directly under exposed roof condition. In order to reduce the overheating of the roof surface a composite combination of reflecting-cum-insulating (R-I) material was developed. The sustainable materials viz., expanded polystyrene (construction waste), saw dust (industrial waste), and the false ceiling panels prepared from industrial waste were used for the development of sustainable R-I material. The R-I material was retrofitted over the existing roof of a model room in an educational building over composite climate (Nagpur, India) and was analyzed experimentally for the period of a year. The thermal resistance of the overall roof assembly was increased from 0.28 to 0.55 m² K/W, which in turn helped to achieve 16% of the duration of the year under thermal comfort. The developed R-I material has also an advantage of low cost (INR 900 per sq. m.) of installation as well as light weight (50 kg/m²) retrofitting solution. The R-I product can further be applied on larger roof areas by the designers to reduce the cooling load of the built environment as well as increase the occupants comfort over the local climatic zone.