The article presents results of studies of silicon – molybdenum cast iron (4.42% Si, 2.59% Mo and 2.48% C wt.-%) crystallization process. Metallographic analysis was carried out using SEM-scanning electron microscopy with the EDS system. In order to determine the phase composition, X-ray diffraction studies were performed. Thermo-Calc, a computer simulation program, was used to simulate the crystallization process. . The obtained data allowed to describe the effect of some elements on the crystallization process. The silicon phase of MnSi could not be identified during metallographic studies. Also, computer simulation of the crystallization process did not answer the question at which point the silicon phase of MnSi crystallizes in the tested alloy. Therefore, not all results obtained were linked to the registered crystallization process (TDA process). The EDS analysis revealed an unusual distribution of molybdenum in the microstructure of the sample, where it is clearly visible that the area enriched with this element is also the separation of spheroidal graphite. The possibility of occurrence of Mo-rich micro-areas found in graphite is considered. The case is debatable and difficult to resolve at this stage. Perhaps, at such a high concentration of molybdenum (2.59% Mo) in the alloy, conditions are created for simultaneously crystallization of graphite and molybdenum phases.