Structure and dynamics of a hydrated white cement were investigated by the T1-weighted lineshape, two-dimensional (2D) exchange, and 2D separation of inhomogeneous and homogeneous lineshapes nuclear magnetic resonance (NMR) techniques. T1 weighting of the proton spectrum eliminates the strong bulk water signal from the pores so that the weaker spectrum of the solid cement matrix becomes observable. The proton spectrum of the solid cement fraction exhibits a characteristic Pake doublet shape and shows a close similarity to the powder spectra of pure calcium hydroxide and the crystalline water of gypsum. The 2D exchange NMR spectrum of white cement demonstrates the existence of slow chemical exchange processes of protons in the solid matrix on a sub-kHz frequency scale. This exchange is orders of magnitude slower than the exchange between the surface and bulk water. The 2D NMR separation of inhomogeneous and homogeneous lineshapes technique demonstrates that the absorption lines of a set white cement are inhomogeneously broadened due to the existence of a distribution of static local magnetic fields. The major contribution to these fields comes from the dipolar fields of the paramagnetic electrons whereas the magnetic susceptibility differences of the liquid and solid fractions add a small part at the solid-liquid boundary where the direction of the external magnetic field is changed. © 1998 American Institute of Physics.