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In 2022, Beller and coworkers achieved the reversible hydrogenation of CO₂ to formic acid using a Mn(I)–PN⁵P complex with excellent activity and reusability of the catalyst. To understand the detailed mechanism for the reversible hydrogen release–storage process, especially the effects of the transition metal center in this process, we employed DFT calculations according to which Ru(II) and Fe(II) are considered as two alternatives to the Mn(I) center. Our computational results showed that the production of formic acid from CO₂ hydrogenation is not thermodynamically favorable. The reversible hydrogen release–storage process actually occurs between CO₂/H₂ and formate rather than formic acid. Moreover, Mn(I) might not be a unique active metal for the reversible hydrogenation of CO₂ to formate; Ru(II) would be a better option.