When processing low-quality gibbsite–kaolinite bauxites, technologies that involve different methods of mechanical and chemical enrichment with the separation of a difficult-to-utilize fine kaolinite fraction for disposal are used. Before production, problems related to waste storage and disposal arise. To solve the problem of utilization, it is necessary to develop an effective technology for the selective processing of the kaolinite fraction. The efficiency of the technology will depend on the quality of pretreatment of raw materials prior to processing for Al₂O₃ extraction. Preliminary preparation of kaolinite fraction is associated with the maximum removal of excess silica during chemical enrichment by treatment with an alkaline solution. The presence of silica reduces the quality of final alumina products and requires a large consumption of reagents during the desiliconization of aluminate solutions. During the chemical enrichment of kaolinite fraction in alkaline solution, a serious problem of the co-dissolution of Al₂O₃ with silica arises. The solution to this problem can be the transformation of phase composition with the transformation of kaolin into a chemically resistant compound corundum, which will create conditions for the selective removal of silica. Kazakhstan’s alumina refinery, Pavlodar Aluminum Smelter, processes low-quality gibbsite–kaolinite bauxite from the Krasnogorsk deposit. To improve the quality of bauxite, preliminary gravity enrichment is carried out to separate the kaolinite fraction to a quantity greater than 50%. The purpose of this work was to study the possibility of the selective processing of the kaolinite fraction via various techniques, including preliminary thermal transformation, through sintering, chemical enrichment, autoclave leaching in a circulating aluminate solution, and low-temperature desiliconization, to obtain a solution for decomposition. As a result of this study, the possibility of obtaining a corundum phase after sintering at a temperature of 900–1000 °C was established, which made it possible to obtain 58.8% chemical enrichment through the extraction of SiO₂ into solution. Further use of the enriched kaolinite fraction in autoclave leaching in a circulating aluminate solution with low-temperature desiliconization made it possible to obtain an aluminate solution with a caustic modulus of 1.65–1.7, which is suitable for decomposition.