Proton spin-lattice relaxation and H-1 NMR spectroscopic data are used for studies of the water adsorption and morphology of several newly synthesized carbon-based chars. Two NMR lines have been observed in accordance with a difference between macropore and micropore water in a system with heterogeneous pore structure. The macropores occupy about the half of the char particle volume. In aqueous suspension fast molecular exchange between water in macropores and bulk water leads to an intense NMR line with a single spin-lattice relaxation time T-1, which exhibits a strong particle size effect. This effect has been used for the estimation of T-1 of water molecules in the vicinity of paramagnetic centers at the surface of chars, as well as for macropore size estimation. The kinetics of water vapor adsorption in chars as seen by H-1 NMR indicates that this process begins in micropores, which serve as primary adsorption centers. Water molecules in micropores exhibit specific properties which are characteristic of liquids in a small, restricted space, and they give rise to the observed accumulation as well as saturation effects.