In this work, a density functional theory (DFT) study was performed to identify the catalytically active species in the copper-catalyzed three-component reductive hydroxymethylation of styrene with CO2 and hydrosilane. The calculations reveal that the dimeric copper(I) hydride species, formed in a mixture of the bisphosphine ligand, Cu(OAc)(2), and hydrosilane, probably acts as the catalyst precursor. In the beginning, this species is catalytically competent to trigger the hydrocupration of styrene, along with the formation of the dimeric copper(I) alkyl intermediate. Subsequently, CO2 insertion into the dimeric copper(I) alkyl intermediate occurs, which is accompanied by the cleavage of the Cu-Cu bond and the generation of the monomeric copper(I) carboxylate intermediate. In the end, the sequential reduction of the monomeric copper(I) carboxylate intermediate with the hydrosilane produces the monomeric copper(I) hydride species as the actual catalyst and turns on the catalytic cycle. On the other hand, the monomeric copper(II) hydride species, yielded as the kinetic product in the initial reaction of the bisphosphine ligand, Cu(OAc)(2), and hydrosilane, is also reactive for the hydrocupration of styrene. However, the resulting monomeric copper(II) alkyl intermediate is found to be the catalyst resting state, because of the much higher energy barrier demanded for the subsequent nucleophilic attack toward CO2. On the basis of the results of an activation-strain model (ASM) analysis and charge decomposition analysis (CDA), the low activity of the monomeric copper(II) alkyl intermediate can be ascribed to the more crowded environment around the central copper(II) ion and the weaker nucleophilicity of the alkyl moiety. Furthermore, all of the possible CuH species generated in the system are competent to promote the two-component hydrosilylation of CO2 with hydrosilane, which is an inevitable side reaction along with the reductive hydroxymethylation of styrene with CO2 and hydrosilane.