The primary objective of this study was to determine how differences in the composition of the binder made with Portland cement, slag and/or fly ash affect the modification of the cement paste structure and the properties of concrete with respect to its freeze/thaw resistance. The test results show that the use of mineral additions (fly ash or a mixture of fly ash and slag) does not guarantee the impermeability and the frost resistant structure of concrete. The concrete behaves as expected up to the slag level of 20% by mass of the cement. The results from the tests conducted on non-air entrained concretes with W/B ratio of 0.45 (limiting value for concrete exposure class XF4) show that the concrete mix in any case should be air entrained when mineral additions are to be used.