By combining a newly developed two-color laser pulsed field ionization-photoion (PFI-PI) source and a double-quadrupole–double-octopole (DQDO) mass spectrometer, we investigated the integral cross sections (σs) of the vanadium cation (V⁺) toward the activation of CO₂ in the center-of-mass kinetic energy (E_cm) range from 0.1 to 10.0 eV. Here, V⁺ was prepared in single spin–orbit levels of its lowest electronic states, a⁵D_J (J = 0–4), a⁵F_J (J = 1–5), and a³F_J (J = 2–4), with well-defined kinetic energies. For both product channels VO⁺ + CO and VCO⁺ + O identified, V⁺(a³F_2,3) is found to be greatly more reactive than V⁺(a⁵D_0,2) and V⁺(a⁵F_1,2), suggesting that the V⁺ + CO₂ reaction system mainly proceeds via a “weak quintet-to-triplet spin-crossing” mechanism favoring the conservation of total electron spins. In addition, no J-state dependence was observed. The distinctive structures of the quantum electronic state selected integral cross sections observed as a function of E_cm and the electronic state of the V⁺ ion indicate that the difference in the chemical reactivity of the title reaction originated from the quantum-state instead of energy effects. Furthermore, this work suggests that the selection of the quantum electronic states a³F_J (J = 2–4) of the transition metal V⁺ ion can greatly enhance the efficiency of CO₂ activation.