In this study, aluminium fluoride trihydrate (AlF3⋅3H2O) was used to inhibit the sintering of calcined coal-series kaolin (CCSK). In addition, the oil absorption properties of CCSK were studied. The particle-size distribution, specific surface area and porosity of the samples were investigated as a function of calcination temperature and the addition of AlF3⋅3H2O. Moreover, the ability of AlF3⋅3H2O to improve the oil absorption of CCSK was explored. The morphology, structure and phase composition of the specimens were investigated using scanning electron microscopy and X-ray diffraction. The phase transition during heating of the samples was studied using thermogravimetric analysis. The preparation with 10 wt.% AlF3⋅3H2O had the optimal sintering inhibition effect on CCSK at 1000°C. The release of SiF4 gas during heating and the formation of mullite whiskers on the particle surface caused by AlF3⋅3H2O moderated the formation of molten-phase liquid bridges between particles and inhibited sintering of the raw material powder. Furthermore, the formation of submicron mullite whiskers on the surface of the CCSK particles enhanced the oil-absorption properties of the sample significantly.