High-energy X-ray diffraction was employed to study the structural characteristics of a set of C-S-H samples with 0.6 ≤ C/S a;circ 1.75. It has been observed that Si is tetrahedrally coordinated to O for all samples irrespective of chemical composition and the Ca-O coordination number gradually decreases from ∼7 to ∼6 with increasing C/S ratio. This suggests that the C-S-H structure evolves from a tobermorite-like structure into a jennite-like structure as a function of increasing C/S ratio as the interlayer space decreases from ∼1.3 to ∼1 nm. Evolution of these short- and medium-range order structural characteristics in the C-S-H system is associated with the alteration of the Ca-O layers and silicate depolymerization with increasing C/S. © 2011 The American Ceramic Society.