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Further stringent emission legislation requires advanced technologies, such as sophisticated engine management and advanced catalyst and substrate to achieve high catalytic performance, especially during the light-off phase. This paper presents the results of calculations and measurements of hydrocarbon and carbon monoxide light-off performance for substrates of different wall thickness, cell density and cell shapes. The experimental data from catalyst light-off testing on an engine dynamometer are compared with theoretical results of computer modeling under different temperature ramps and flow rates. The reaction kinetics in the computer modeling are derived from the best fit for the performance of conventional ceramic substrate (6mil/400cpsi), by comparing the theoretical and experimental results on both HC and CO emissions. The calibrated computer model predicts the effects of different wall thickness, cell density and cell shape.