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The three-way-catalyst (TWC) is an essential part of the exhaust aftertreatment system in spark-ignited powertrains, converting nearly all toxic emissions to harmless gasses. The TWC’s conversion efficiency is significantly temperature-dependent, and cold-starts can be the dominating source of emissions for vehicles with frequent start/stops (e.g. hybrid vehicles). In this paper we develop a thermal TWC model and calibrate it with experimental data. Due to the few number of state variables the model is well suited for fast offline simulation as well as subsequent on-line control, for instance using non-linear state-feedback or explicit MPC. Using the model could allow an on-line controller to more optimally adjust the engine ignition timing, the power in an electric catalyst pre-heater, and/or the power split ratio in a hybrid vehicle when the catalyst is not completely hot.