The syntheses of kaliophilite have been carried out from the starting materials of near kalsilite compotions (KAISiO4), of which the AI2O3/SiO2 ratio is greater than 1/2. The X-ray powder deffraction pattern fit well to those of previous investigators. The crystal structure of synthetic kaliophilite was proposed by using the model consisting of four different types of kalsilite structure. The positions and intensities of the X-ray powder pattern were able to be explained on the basis of these four domains, belonging to thr twinning by merohedory. As a result of the conditions of the syntheses, it may be supposed that the violation of the AI-O-AI avoidanice rule can possibly exist along the domain boundaries.