Flue Gas Desulfurization Gypsum (FGDG), an industrial by-product generated by power plants, was thermally treated and incorporated in cement-free fly ash bricks. This study aimed to determine the effects of using a thermally treated FGDG as an additive to improve the mechanical and structural properties of cement-free fly ash bricks. FGDG was thermally treated for 2 h at different temperatures. The influence of varying amounts (10–50%) of thermally treated FGDG on the performance of cement-free bricks was analyzed through mechanical properties, micrography, durability, the evolution of particle size distribution and environmental characteristics experiments. The effect of curing temperatures and curing age on the strength development and microstructural properties was also investigated. A Toxicity Characteristic Leaching Procedure (TCLP) was carried out to determine the leachability of metals from the synthesized FA cement-free brick. The results showed that the FGDG had a high calcium oxide content. In contrast, FA is mainly composed of silica, and both materials carry cementitious properties making both good raw materials for this study. The FA cement-free bricks containing 30% of thermally treated FGDG, oven-cured at 60 ℃, yielded the highest unconfined compressive strength (UCS) of 7.14 MPa. However, curing at ambient temperature for 28 days yielded a better UCS of 7.37 MPa. The particle size distribution showed that particles transformed from fine particles at 7 days to larger particles at 28 days due to particle growth. Durability tests showed that the developed bricks could withstand 7 wet/dry cycles. The TCLP showed that the leachability concentrations of all metals are within the limit and, therefore, can be potentially used as a building material in backfilling. The synthesis of FA/FGDG composite will aid in reducing the generated waste gypsum in landfills consequently eradicating human health challenges and loss of biodiversity. This paper showed that developing FA/FGDG composites will reduce their environmental impact and make them a resource for other valuable products such as backfilling applications and green building bricks.