Numerical simulations of heat- and mass-transfer and heterogeneous reactions in catalytic monoliths are reported with the focus on the influence of radiation heat transfer on the thermal behavior of the monolith. Appropriate heterogeneous kinetics and boundary conditions were calculated for two cases including: an automobile catalytic converter in which carbon monoxide is oxidized over a platinum (Pt) catalyst and a catalytic combustor for gas turbine power generation in which methane is oxidized over a palladium oxide (PdO) catalyst. Surface oxidation rates of carbon monoxide are based on measurements of Pt catalyst activity in a catalytic flow reactor, and rates for methane oxidation are based on reaction kinetics for a supported PdO catalyst assigned from differential reactor measurements. These simulations show that in the high aspect ratio passageways (length to diameter) in catalytic monoliths, radiation heat transfer can play a major role in the energy balance on the catalytic surfaces, which determines the transient warm-up behavior and the steady-state location of catalyst light-off. For gray surfaces, however, the predicted steady-state and transient behaviors are not sensitive to the emissivity of the monolith walls.