Kaolin, theoretically known as having low reactivity during geopolymerization, was used as a source of aluminosilicate materials in this study. Due to this concern, it is challenging to directly produce kaolin geopolymers without pre-treatment. The addition of ground granulated blast furnace slag (GGBS) accelerated the geopolymerization process. Kaolin-GGBS geopolymer ceramic was prepared at a low sintering temperature due to the reaction of the chemical composition during the initial stage of geopolymerization. The objective of this work was to study the influence of the chemical composition towards sintering temperature of sintered kaolin-GGBS geopolymer. Kaolin-GGBS geopolymer was prepared with a ratio of solid to liquid 2:1 and cured at 60 °C for 14 days. The cured geopolymer was sintered at different temperatures: 800, 900, 1000, and 1100 °C. Sintering at 900 °C resulted in the highest compressive strength due to the formation of densified microstructure, while higher sintering temperature led to the formation of interconnected pores. The difference in the X-ray absorption near edge structure (XANES) spectra was related to the phases obtained from the X-ray diffraction analysis, such as akermanite and anothite. Thermal analysis indicated the stability of sintered kaolin-GGBS geopolymer when exposed to 1100 °C, proving that kaolin can be directly used without heat treatment in geopolymers. The geopolymerization process facilitates the stability of cured samples when directly sintered, as well as plays a significant role as a self-fluxing agent to reduce the sintering temperature when producing sintered kaolin-GGBS geopolymers.