Fine-grained and mainly reddish color, compact and slightly breccious and vesicular pyrometamorphic rocks (natural clinker) are associated to the spontaneous combustion of coal seams of the Cerrejon Formation exploited by Carbones del Cerrejon Limited in La Guajira Peninsula (Caribbean Region of Colombia). These rocks constitute remaining inorganic materials derived from claystones, mudstones and sandstones originally associated with the coal and are essentially a complex mixture of various amorphous and crystalline inorganic constituents. In this paper, a petrographic characterization of natural clinker, aswell as the application of the X-ray diffraction (Rietveld method) by mean of quantitative analysis of its mineral phases were carried out. The RIQAS program was used for the refinement of X ray powder diffraction profiles, analyzing the importance of using the correct isostructural models for each of the existing phases, which were obtained from the Inorganic Crystal Structure Database (ICSD). The results obtained in this investigation show that the Rietveld method can be used as a powerful tool in the quantitative analysis of phases in polycrystalline samples, which has been a traditional problem in geology.