Mexico has important kaolin deposits, which must be assessed to obtain products with a high commercial value, such as kaliophilite as raw material for biodiesel production. Two kaolins, A and B, with approximate SiO2:Al2O3 ratios of 1 and 1.2, respectively, were used as raw materials to produce kaliophilite. Both kaolins were obtained from the municipality of Agua Blanca in the State of Hidalgo, Mexico. Kaolins are a source of Al and Si for the synthesis of kaliophilite through an alkali fusion process at 700 °C followed by ultrasonic treatment at 28 kHz to different times and for Kaolin-KOH ratios of 1:1 and 1:1.2 (mass: mass). The kaolins as received and the alkaline mixtures heat and ultrasonically treated were analyzed using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), and scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS). The most suitable kaolin for synthesizing kaliophilite was kaolin A with the Si/Al mass ratio of approximately 1, which exhibited a higher crystallinity index range from 54 to 79.6%. Higher KOH concentrations promote the amorphous material formation decreasing the kaliophilite amount. The crystallinity index was increased when the time of ultrasonic treatment was increased.