This investigation describes the results of an experimental and numerical research project aimed at comparing mileage and CO2 emissions from two different commercial versions of Daimler AG Smart ForTwo car: conventional (gasoline) and electric (ED). The investigation includes numerical simulations with the AVL CRUISE software package and on-board acquisitions. A data acquisition system has been designed for this purpose and assembled on board of the Smart ED. The system is composed by a GPS antenna with USB interface, two current transducers, a NI-DAQ device and a netbook computer with a LabView-VI. This system provided on-board information about driving cycle and current flows, gathered simultaneously by GPS, transducers and NI-DAQ. The system was also used to evaluate the losses of energy during the recharge of the electric car. The two cars have been tested over a wide range of driving conditions related to different routes, traffic conditions and use of on-board accessories (i.e. Air Conditioning and radio). The CO2 emissions have been evaluated with a Well-to-Wheel approach.