Thermal dehydration of dicalcium aluminate hydrate, C(2)AH(8), has been investigated by simultaneous differential thermal and thermo gravimetric analysis (DTA/TGA), powder X-ray diffraction (XRD), temperature-dependent infrared spectroscopy (FT-IR), and BET method of surface area measurement. The temperature-dependent infrared measurements were studied by two-dimensional infrared (2D-IR) correlation spectroscopy. The structure of aluminum-oxide polyhedron, characterized by Al-27 solid state NMR spectrum method and FT-IR, shows tetrahedron and octahedron as the main forms of aluminum-oxide polyhedrons in C2AH8 sample. From the results obtained a variety of structural transformations observed are explained as a consequence of the removal of loosely held interlayer water molecules at lower temperatures, followed by grafting process of the interlayer [Al(OH)(4)](-) anion. Structural model of a grafting process of the interlayer [Al(OH)(4)](-) tetrahedron onto hydroxylated octahedrons of [Ca2Al(OH)(6)](+) layers has been proposed in order to explain observed loss of one water molecule, shrinkage of interlayer spacing and qualitative changes of FT-IR spectra. At higher temperatures the dehydroxylation of the lattice and decomposition of the interlayer species occurs, yielding amorphous material that crystallizes into C(3)A and C(12)A(7) at 885 degrees C. Those findings provide improvement in the interpretation of thermo-analytical results of calcium aluminate cements (CAC) hydration products, and better understanding of CAC conversion process. (c) 2007 Elsevier B.V. All rights reserved.