The local structure in [EMI][TFSI] and EC/DMC co-solvent mixtures was analyzed in terms of the most representative atom-atom pair RDF, SDF and CDF in order to analyze and provide an insightful average picture of the IL/carbonate structure. The RDF for center-of-mass Li + [TFSI] - peaks showed the presence of Li + -[TFSI] -interaction, and this interaction increased with increase in carbonate concentration signifying the presence of strong Li + [TFSI] -interactions at higher carbonate content. Further to our analysis of the Li + [TFSI] -complex, we also calculated the RDFs between nitrogen (N 1 ) and oxygen (O 1 ) atoms of the [TFSI] -anion and the Li + ion, and the intensity of the RDF peaks increased with increase in EC/DMC content. According to the radial distribution functions, for the [EMI] + cation ring centers, very weak but clear ordering was observed. A first and a second coordination shell were identified. The ordering between the cations has been enhanced by the addition of carbonate in the mixture. The [TFSI] -anions showed even a weaker ordering towards each other. Similar to the phenomenon observed for [EMI] + ring centers, The intensity (height) of the peak for the [TFSI] -anions center-of-mass increased by the addition of carbonate in the mixture. According to the RDFs, the addition of EC/DMC solvents into [EMI][TFSI] IL provides a more structured system than the pure [EMI][TFSI] IL system in terms of first peak heights and longer-range higher neighbor shell. The interaction between the O 1 /N 1 atom of [TFSI] -and H 1 atom of [EMI] + fpound to increase with increase in carbonate concentration. The result from the spatial distribution functions (SDF) showed that, in the pure ionic liquid, adjacent cations were almost exclusively located on top and below the [EMI] + ring, whereas the [TFSI] -anions mainly coordinated to the cation within the ring plane. The [TFSI] -anions occupied both the on top position and in plane position in the [EMI] + ring. With increasing carbonate content, however, the large amount of carbonate disturbed the original near ordering which was found in the pure ionic liquid.