Ionic liquids, a class of alternative solvents, are known for their ability to capture carbon dioxide (CO2). The understanding of the role of the individual ionic entity of the ionic liquid (IL) and the involved mechanism is essential to design a better solvent for the capture process. In the present study, we employed density functional theory based electronic structure calculations and metadynamics method based first-principles molecular dynamics (FPMD) simulations to investigate the roles of the cation and anion of the IL by analyzing the energetics and free energy profile of the involved chemical reactions. The mechanism of chemisorption of CO2 by the aprotic N-heterocyclic and phenolate anions paired with tetrapropyl phosphonium cation [P3333] were studied to understand the reaction mechanism of the initial capture process. The process of uptaking of CO2 by the [P3333][1,2,4-Triz] was studied by the first-principles calculations. The transition states in the reaction pathways were computed by the synchronous transit-guided quasi-Newton method and confirmed by the intrinsic reaction coordinate calculations using first-principles simulations. The dynamics of the energetics of the chemisorption process were studied by constructing the free energy surface using metadynamics-based FPMD simulations. First, the nucleophilic center was generated at the α-carbon of the cation by transferring a proton to the anion with the formation of the phosphorus ylide. The formed cation ylide chemisorbs CO2 through the formation of a bond between the α-carbon of ylide and the carbon of CO2. The direct addition of CO2 to the anion of the ionic pair was studied as the second pathway. We find that the chemisorption of CO2 by the anion is more favorable than that by the cation. By comparing the chemisorption of CO2 by the ions, we observe that the deprotonation of the alkyl chain is the more deciding factor, which depends on the basicity of anion and the length of the alkyl chain. We computed the free energy landscapes for the ionic pairs by varying another four anions like cyclohexanolate, 2,4,6-trifluorophenolate, imidazolate, and benzotriazolide paired with tetrapropyl phosphonium cation. The effect of the alkyl chain on the proton transfer was studied by tetrabutyl and tetrapentyl phosphonium cations paired with 1,2,4-triazolide anion. The carbonated product, formed from the anion, is thermodynamically controlled, while the carboxylated product (formed from cation) is kinetically controlled. We hope that our findings will enhance the knowledge of the selectivity of ionic entities for designing IL-based solvents for the capture process of CO2.