Nowadays, nuclear power plants are widespread around the world and research is of great interest. Together with nuclear research, shielding of different types of radiation is an important current topic of research aiming at their safety. Portland cement has been an elementary building material for centuries. Since barium is very efficient in shielding different types of radiation, it can be assumed that the radiation shielding capability of cement can be improved by incorporation of barium. This work deals with the influence of barium oxide, added in the form of barium carbonate and sulphate, on the formation and properties of Portland clinker. The structure of burnt clinkers and the ratio of clinker phases were studied by polarizing microscopy and by X-ray diffraction. With increasing barium content, the alite-belite ratio decreases and the content of free lime gradually increases. Moreover, sulphates induce the growth of alite crystals. The ability of barium to be a part of the clinker minerals was observed by scanning electron microscopy. Belite and clinker melt contain the highest amount of barium, but aggregates of barium oxide are formed in the clinker melt. Furthermore, the rate of alite crystallization was studied under isothermal conditions.