Single-component epoxy cement system is an interesting material used in construction engineering, and it is different from traditional two-component epoxy-cement system. We studied the interaction mechanism of single-component epoxy-cement system only in the range of macro mechanical performances, and used the cement and single-component epoxy directly to investigate the interaction between the both. Solid-state13C NMR, FT-IR, Raman spectroscopy and XRD were employed to trace the change of the system. Results showed that the epoxide rings in cementitious environment had been opened by cement ingredients. It was true that single-component epoxy could be used as reactive additive in cementitious system.