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The aim of this study is to investigate the parameters influencing the real driving emission monitoring with particular attention towards the influence of road gradient. For this purpose, an experimental activity was carried out with a Euro 5 Diesel light-duty vehicle, driven along two tracks of Naples characterized by a different road gradient: the first pattern is quite flat, the second includes positive (+2.9%) and negative (−3.6%) road gradient. Exhaust emissions of CO, THC, NOx, CO2 were acquired on road by using a portable emission measuring system (PEMS) connected also to the Engine Control Unit for saving the main engine parameters and to the GPS for the geographical coordinates and altitude. The acquired speed profiles were repeated on the chassis-dynamometer without simulating the road gradient.