An experimental and computational mechanistic investigation of the key carboxylation step in copper(I)-catalyzed boracarboxylation of vinyl arenes is presented here. Catalytically relevant intermediates, including a series of Cu<sup>I</sup>-spiroboralactonate complexes, with electronically differentiated vinyl arenes and stabilized by the NHC ligand IPr (IPr = 1,3-Bis(2,6-di-isopropylphenyl)-4,5-dihydroimidazol-2-ylidine), were isolated and characterized. In situ <sup>1</sup>H NMR timecourse studies and subsequent Hammett analysis (<i><sub>p</sub></i>) of carbon dioxide addition to (β-borylbenzyl)copper(I) complexes (benzyl = CH<sub>2</sub>Ar<sup>p-X</sup>) revealed a linear correlation with a negative rho (<i>ρ</i>) value. Density functional theory (DFT) calculations support a direct CO<sub>2</sub> insertion as the primary mechanism for electron-rich benzyl-copper carboxylation. Kinetically sluggish carboxylation of electron-poor trifluoromethyl-substituted benzyl-copper complex (benzyl = CH<sub>2</sub>Ar<sup>p-CF</sup><sup>3</sup>) was accelerated upon addition of exogenous PPh<sub>3</sub>. Conversely, the additive inhibited reactions of electron-rich tert-butyl-substituted benzyl-copper complex (benzyl = CH<sub>2</sub>Ar<sup>p-tBu</sup>). These kinetic observations implied that a second carboxylation pathway was likely operative. DFT analysis demonstrated that prior binding of the electron-rich phosphine additive at (β-borylbenzyl)copper(I) yields a meta-stable intermediate that precedes an S<i><sub>E</sub></i>-carboxylation mechanism, which is kinetically favorable for electron-deficient benzyl-copper species and circumvents the kinetically challenging direct insertion mechanism. The mechanistic picture that emerges from this complementary experimental/computational study highlights the kinetic complexities and multiple pathways involved in copper-based carboxylation chemistry.