Issues concerning mechanisms of durability of hydrated cement phases in aggressive environments were studied. The possibility of using organic compounds in order to modify the micro- and nanostructure of the calcium-silicate-hydrate (C-S-H) phases was also investigated. Pure cement-based hydrated phases were synthesized and characterized by several analytical techniques such as X-ray diffraction, thermal gravimetric analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. Compacted samples of the synthetic hydrated cement phases were also prepared and used for the assessment of durability and mechanical properties. This doctoral thesis is comprised of several research chapters which can be categorized into two main parts. The first part focuses on the development of novel organically modified C-S-H systems. The second part involves the mechanisms underlying the volume stability of phase pure sulfoaluminate and related phases. A brief description of each part is as follows: - development of novel organically modified C-S-H systems: The mechanisms of interaction of organic compounds with the nanostructure of C-S-H systems were studied. A model for the nanostructure of the resulting composite systems was proposed. In addition, the organically modified systems were tested for length-change, calcium-ion leaching and diffusion of isopropanol. Dynamic mechanical analysis and microindentation techniques were also used to determine the mechanical performance. Evidence of the superior engineering performance of the novel organically modified C S-H systems was provided. - mechanisms of the volume stability of sulfoaluminate and related phases: Volume stability and change in the microstructure of the synthetic ettringite, monosulfate and thaumasite was critically examined in de-ionized water as well as in highly concentrated gypsum- or lime-water. A new dissolution-based mechanism for the expansion of these phases was proposed. The volume stability of multicomponent systems comprised of the C-S-H-based system (prepared in part I) and these sulfate-based hydrated phases was also investigated. It was suggested that the systems containing the modified C-S-H rather than the phase pure C-S-H had better resistance to crack growth and disintegration originating from the presence of ettringite or thaumasite.