Insight into mechanisms of heterogeneously catalyzed reactions holds importance in the development and optimization of new catalytic materials. Yet, the approaches often used in such investigations heavily rely on assumptions concerning the reactor and kinetics. Herein we report a new kind of kinetic investigation taking CO₂ hydrogenation reaction, specifically the reverse water–gas shift (RWGS) reaction over 3 wt% Pt/CeO₂, as an exemplifying case. The reported approach is based on spatially resolved steady-state isotopic transient kinetic analysis (SSITKA) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) identifying gaseous/surface species and their spatial variations along the reactor. This approach allows accurate evaluation of reaction mechanism by identifying correlations among the concentrations of gaseous/surface species and by quantitative description of their spatial variations by a kinetic model. Spatially resolved SSITKA-DRIFTS experiments show carbonate decomposition via a Pt-bound carbonyl to be the main route towards the production of carbon monoxide. Further kinetic modeling of the spatially resolved data confirms this mechanism proposal, and points to the production of water as the rate-limiting step.