The hoisted increment in the CO2 emission in the atmosphere is a noteworthy environmental problem. Gas-liquid absorption is a well-known strategy that can be used to control CO2 emissions from an increased rate of fossil fuel industrializations. In this work, a combination of broadband dielectric spectroscopy, Fourier infrared (FTIR) spectroscopy, and quantum chemical calculations were used to study the absorption, desorption and kinetic mechanism of a room temperature imidazolium ionic liquid (IL) with cyanide anion, 1-ethyl-3-methylimidazolium thiocyanate ([EMIM][SCN]) on CO2 exposure. Initially, the charge transport and glassy dynamics of [EMIM][SCN] is investigated in a wide frequency and temperature range using broadband dielectric spectroscopy and differential scanning calorimetry. The conductivity relaxation was well fitted with Havriliak-Negami function in the modulus formalism, while the dc conductivity correlated well with the Barton-Nakajima-Namikawa relation. Then, the conductometric approach was taken to monitor the interplay between the ionic conductivity of [EMIM][SCN] and diffusion of captured CO2 in it. The resistance of the IL increases upon CO2 exposure, indicating a chemical change at the molecular level of [EMIM][SCN]. The possible CO2 capturing mechanisms for [EMIM][SCN] were investigated with density functional theory calculations and FTIR spectroscopy. Thus, this work proposes a new strategy to explain the mechanism underlined in chemisorption of CO2 in the [EMIM][SCN]. This can be extended to more promising CO2 capturing materials including ionic liquids especially imidazolium-based ionic liquids with cyanide anions like dicyanimide, tricyanometanide, tetracyanoborate, etc.