Epitaxial silicene, which is one single layer of silicon atoms packed in a honeycomb structure, demonstrates a strong interaction with the substrate that dramatically affects its electronic structure. The role of electronic coupling in the chemical reactivity between the silicene and the substrate is still unclear so far, which is of great importance for functionalization of silicene layers. Here, we report the reconstructions and hybridized electronic structures of epitaxial 4 3 4 silicene on Ag(111), which are revealed by scanning tunneling microscopy and angle-resolved photoemission spectroscopy. The hybridization between Si and Ag results in a metallic surface state, which can gradually decay due to oxygen adsorption. X-ray photoemission spectroscopy confirms the decoupling of Si-Ag bonds after oxygen treatment as well as the relatively oxygen resistance of Ag(111) surface, in contrast to 4 3 4 silicene [with respect to Ag(111)]. First-principles calculations have confirmed the evolution of the electronic structure of silicene during oxidation. It has been verified experimentally and theoretically that the high chemical activity of 434 silicene is attributable to the Si p(z) state, while the Ag(111) substrate exhibits relatively inert chemical behavior.