H-1 nuclear magnetic resonance (NMR), supported by a measurement of the degree of hydration using X-ray diffraction, has been used to fully characterise the nano-scale porosity and composition of calcium-silicate-hydrate (C-S-H), the active component of cement. The resultant "solid" density and composition are rho = 2.68 g/cm(3); (Ca)(1.53)center dot(Si-0.96,Al-0.04)O-3.51 center dot(H2O)(1.92) for an underwater cured, never-dried cement paste with an initial mix water-to-cement ratio of 0.4 after 28 days of hydration. In addition, the first pore-type resolved desorption isotherm of cement that shows the location of water as a function of relative humidity has been measured. Critical to our results is verification of the assignment of the different NMR spin-spin relaxation time components. These have been corroborated with conventional analyses. The new methodology is key to enabling design of cement pastes with lower environmental impact. (C) 2013 Elsevier Inc. All rights reserved.