Research on the development of a homogeneous process for low-temperature oxidation of carbon monoxide in the presence of a “platinum group metal + vanadium-containing heteropolyacid (HPA)” catalytic system has been presented. The optimal reaction conditions, ensuring the maximum rate of CO oxidation to CO2, have been determined; for this reaction the kinetic features have been established, and its mechanism has been proposed. It has been shown that homogeneous systems based on PdII complex exhibit high activity and productivity, but have low stability and operate only at pH below 1,5. The stability of the catalyst can be increased by simultaneous introduction of σ- and π-donor ligands into the system; however, it is more effective to use the PtIV complex in the presence of catalytic amounts of palladium salt at a ratio of 100/1. The transition from HPA solutions with a low content of vanadium atoms (H7PMo8V4O40) to solutions of modified compositions (H10P3Mo18V7O84) ensures an increase in the activity and productivity of the system, with the kinetics of CO oxidation being maintained. The combined homogeneous catalyst PtIV + PdII + H10P3Mo18V7O84 remains stable during multi-cycle use without reducing activity, operates without an induction period and can be used at pH range of 1,7–2,0, which simplifies the process equipment.