Polymer modification in the field of construction engineering has a history nearly 90 years. Mechanical properties, water resistance, chemical resistance and durability to some extent have been improved by different polymer modification although those modifications are classified into physical modification. To obtain better performance of cementitious materials, chemical modifications have been tested. In this study, epoxy has been designed as a predominant modifier in the modified system with its corresponding hardener. Amino sulfonate, the additive, has been used to improve the system’s workability. Functional silane, as it has special functional groups, was used to set up the connections among epoxy, cement moiety and amino sulfonate. The investigation carried out by IR, Raman spectroscopy, DSC and NMR reveals that the chemical connections have been set up among all the components in the modified system. Flexural tests results present the good effect of the chemical modification as the flexural strength and strain have been improved substantially.