Ceramic and metallic three way catalytic converters have been compared to assess the influence of the substrate geometrical and physical parameters on the exhaust gas conversions for several vehicle operating conditions. Both catalysts were placed on a vehicle equipped with a 2.81 DOHC V6 spark ignition engine that was tested on a chassis dynamometer under steady state conditions for several engine speeds and loads. The data obtained include exhaust gas species concentrations and temperature taken both upstream and downstream of the catalytic converter, as well as temperatures in various locations within the substrate of the catalysts. The experimental data revealed that: (i) at low space velocities, the ceramic substrate presents better conversions, particularly for HC and CO, as compared to the metallic substrate, possibly because of its lower thermal conductivity which facilitates local ignition; (ii) at high space velocities, the metallic substrate presents better conversions, as compared to the ceramic substrate, mainly because of its larger geometric surface area and lower transverse Peclet number; and (iii) in general, the HC conversion for small space velocities is kinetically controlled while for high space velocities it is mass transfer limited; both limitations are less pronounced for the CO conversion and insignificant for the NOx conversion. (C) 2007 Elsevier Ltd. All rights reserved.