This dissertation aims to provide a comprehensive understanding of the evolution of solid phase composition with ongoing hydration in OPC‒rich and CAC‒CsHx rich ternary binders. The work is based on a multi‒method approach including XRD, TGA, MAS NMR spectroscopy, calorimetry, microscopy and thermodynamic calculations. From the combinations of results obtained from the different analytical methods, a schematic representation of the phase evolution with ongoing hydration in OPC and CAC‒CsHx rich combinations was achieved, along with plots showing the distributing hydrate phases in the ternary diagram OPC‒CAC‒CsHx. C‒S‒H, portlandite, ettringite and AFm phases stand as main hydration products in the OPC‒rich combinations. C‒S‒H accounts for ~70% of the X‒ray amorphous fraction. In the CAC‒CsHx rich combinations ettringite along with AH3, monosulphoaluminate, strätlingite and hydrogranet phases precipitate. The high portions of X‒ray amorphous fractions in such combinations were mainly attributed to AH3 gel and AFm phases. Additionally, comparison of QXRD results with stoichiometric calculations, thermal analysis and 27Al NMR revealed that a portion of the formed ettringite and portlandite are in an X‒ray amorphous state during hydration. The variation of CAC type and water content strongly influences the hydration mechanism and phase assemblage in the ternary binders, whereas differences in mixtures with different sulphate sources are mainly related to the different dissolution kinetics of the sulphate.