A composite geopolymeric material was synthesized from Bayer red mud combined with granulated blast-furnace slag. Thermal pretreatment was applied to improve the solubility of red mud in alkaline solution to promote geopolymerization. The dissolution efficiencies of alumina and silica reached a maximum when red mud was calcined at 800 degrees C, resulting in the highest compressive strength of binders. It was demonstrated that a higher solubility of calcined red mud led to a higher strength of the composite binders. The characteristic microstructures of hydration products were studied to illustrate the geopolymerization process by XRD, FTIR and SEM. The results showed that aluminosilicates were dissolved in the alkaline solution to form nanostructural particulates during the early dissolution process, and then accumulated to form highly dense geopolymeric matrices through solidification reaction. The coexistence of geopolymer and C-(A)-S-H is suggested to contribute to the good performance of the composite binders.