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In this paper the behavior of the three-way catalyst equipping a 2-liter car is fully analyzed considering exhaust gas and ceramic temperatures trends ( and of related engine parameters) in on-road operations of the car under different traffic conditions. These are classified by means of driving cycles clusters determined by multivariate statistical analysis of car speed and gear usage real profiles, detected on-road by the same car in designed experimental plans. Instantaneous fuel consumption and signals of a linear oxygen sensor, placed up-stream catalyst, have been analyzed to better characterize engine and catalyst performance. Emissions are measured in laboratory performing the most statistically representative driving cycles with car on the dynamometer chassis. The effect of traffic conditions on catalyst behavior and exhaust emissions is analyzed through the study of series of consecutive driving cycles.