Understanding the silicate polymerization of calcium silicate hydrate (C-S-H) gel and its crystalline polymorphs is important in cement science. NMR can determine Si environments, but the measurement can be timeconsuming and provides no spatial information. X-ray absorption near-edge structure (XANES) spectroscopy is a fast tool for probing Si coordination, possibly with spatial information. However, there lacks an understanding of Si K-edge XANES spectra of cement-related silicate phases. Here, a Si K-edge XANES spectral database of nanocrystalline C-S-H, C-S-H minerals, blast-furnace slags, and metakaolin is provided. Si K-edge of C-S-H minerals shifts to higher energies with higher polymerized Si and lower Ca–Si connectivity in the Si second nearest neighbor shell. Si K-edge energy shows weak correlations with Ca/Si ratio, average Si–O bond length, and SiO4 distortion due to the structural complexity of silicates. The substitution of Al for Si shifts the Si K-edge of tobermorite and slags to higher energies.