X-ray photoelectron spectroscopy (XPS) and static contact angle measurements were used to study the interaction between silane coupling agents and cured cement paste. Three different silane coupling agents were investigated: aminopropyltriethoxy silane (APTES), 3-glycidyloxypropyltrimethoxy silane (GPTMS), and methoxy-terminated polydimethxyl siloxane (PDMS). These silanes have different end groups, so the change in surface energy after undergoing a successful reaction between the silane and hydroxyls on the surface of the cement paste was demonstrated by a change in contact angle. Relative to untreated samples, APTES samples decreased the contact angle, PDMS samples increased the contact angle, and GPTMS did not show a significant change in contact angle. Samples with a water-to-cement ratio (w/c) of 0.5 showed a larger change in contact angle than 0.4 w/c ratio samples, because of a greater number of hydroxyl groups at the surface. Deconvolution of the O 1s and Si 2p XPS peaks were performed to determine contributions from bridging and nonbridging atoms. An increase in bridging silicon and oxygen atoms relative to untreated samples indicated successful silane condensation and that a covalent bond was formed between the cement paste and silanes.