Gasoline engine vehicle emissions, such as nitrogen oxides (NOx), CO and hydrocarbons (HCs), are a major source of air pollution, and require improved emission control systems. By-product NH3 and N2O emissions, which come from low N2 selectivity in the emission control system, are also a major concern. The current study has comprehensively investigated the impact of the Pt-substitution in commercial Pd/Rh-based three-way catalyst (TWC) formulations with respect to catalytic performance. TWC performance was systematically evaluated with respect to the warm-up catalytic converter (WCC) and the under-floor catalytic converter (UCC). This included evaluating TWC activity under realistic simulated exhaust conditions including fuel-rich, stoichiometric and fuel-lean (0.99≤λ≤1.01). Pt-substituted TWCs outperformed Pd-based counterparts, regardless of the converter type (WCC or UCC), in CO, C3H6 and C3H8 oxidation and NO reduction reactions under the simulated exhaust conditions tested. Moreover, Pt-substituted TWCs exhibited significant stability upon hydrothermal aging at 1,050 °C. The results show that after aging the Pt-substituted catalyst retained higher N2 selectivity than the Pd-based TWC. Over Pd-based TWCs, N2 selectivity drastically dropped from 70–80% to 15–35% after aging, while Pt-substituted TWCs N2 selectivity dropped from 80–100% to only 60–80%. The key finding from this study is that Pt incorporation in a Pd/Rh TWC improves the emission control from gasoline vehicles in terms of both CO and HC oxidation and NOx reduction.