Sodium-ion batteries (SIBs) have received much attention as promising alternatives to Li-ion batteries as large scale and low-cost energy storage systems owing to close electrochemical similarity between lithium and sodium, and the natural abundance of sodium resources. However, many challenges must be overcome to make SIBs well-positioned in commercialization such as low cyclability, and low stability of the solid-electrolyte interphase (SEI) formation, results from the decomposition of organic solvents in the electrolyte on the anode of SIBs. The SEI has a profound effect on cycle life and performance of the batteries. Therefore, understanding the SEI compositions and its formation mechanisms is crucial for SIBs development. Carbon-based anode materials are commonly used as the anode for SIBs because of their appropriate electrochemical properties, an abundance of carbon and safety. The oxygen-containing groups often present in the carbon-based anode and they usually actively involved in chemical reactions. In this work, we performed density functional theory (DFT) calculations to elucidate the effect of oxygen containing group of epoxy on decomposition mechanisms at the initial stages of sodiation of ethylene carbonate (EC) molecule which is one of common electrolytes applied in ion-battery. The calculation results indicated that EC decompositions on pristine graphene were initiated by CE-OE bond cleavage which is rate-limiting step followed by Cc-OE bond cleavage in the second step producing CO2 and acetaldehyde as products (Figure 1). The presence of an epoxy group on graphene does not directly change the mechanisms, however, it significantly increased the activation barriers on all decomposition pathways compared to those on pristine graphene. The strong electrostatic interaction between negatively charged epoxy group and positively charged Na ion weakens interaction between EC and carbon surface. Also, the presence of an epoxy group facilitates carbon surface to be more positively charged and electron transfer to EC is less favorable than that on pristine graphene. Furthermore, we investigated the solvation effect on the mechanisms by increase the number of EC molecules to model a solvation shell. The results showed that the inclusion of the electrolyte environment reveals other possible decomposition mechanisms including proton transfer from EC molecule to epoxy group producing hydroxyl group on carbon surface prior to the EC ring-opening reaction step. This work suggests that the presence of oxygenated functional group on anode carbon surface and solvent environment can have significant effects on EC decomposition mechanisms both thermodynamic and kinetic aspects. Including the electrolyte solvation shell is crucial for electrolyte decomposition investigation using molecular modeling. Figure 1