The performance of a three-way catalyst (TWC) in natural gas-powered vehicles is enhanced by periodic changes in air-to-fuel ratio (λ-modulation). The reaction networks and sequences inside the catalyst that facilitate such enhanced performance have not been extensively investigated. This work applied intra-catalyst measurements (SpaciMS) to analyze the transient spatiotemporal gas concentrations inside a Pd-based TWC to establish relationships between CH4, NOx, CO and H2 conversion pathways. Steam reforming and partial oxidation were revealed to be the main CH4 conversion routes. The cyclic rich-lean conditions combined with the oxygen storage capacity (OSC) of the TWC generate reduced and oxidized zones that are constantly moving within the catalyst, changing the dominant chemical reactions occurring on the surface. In the reduced zones, OSC is depleted while CH4 is converted through steam reforming and NOx is converted through reactions with H2, CO, and other surface-bound reducing fragments formed by CH4 conversion. In the oxidized zones, OSC is replenished, CH4 is converted by partial oxidation, and H2, CO, and NH3 are oxidized. The length of lean-rich phases impacts the catalyst performance significantly; too short or too long of a rich or lean phase can lower the overall conversion of reactive species. An inhibition of CH4 conversion was observed during the rich phase possibly due to CO-poisoning of active sites. The intra-catalyst measurements revealed that the catalyst consists of three distinct reaction zones and their lengths vary with modulation conditions. Various modulation frequencies, amplitudes, λ-centers, and temperatures were investigated which allowed an understanding of how these parameters affect the reaction zones and catalyst utilization. Understandings from this work can enable adaptive λ-control strategies to optimize the overall TWC performance over a range of vehicle operating conditions.