Transportation, as one of the most growing industries, is problematic due to environmental pollution. A solution to reduce the environmental burden is stricter emission standards and homologation tests that correspond to the actual conditions of vehicle use. Another solution is the widespread introduction of hybrid vehicles—especially the plug-in type. Due to exhaust emission tests in RDE (real driving emissions) tests, it is possible to determine the real ecological aspects of these vehicles. The authors of this paper used RDE testing of the exhaust emissions of plug-in hybrid vehicles and on this basis evaluated various hybrid vehicles from an ecological point of view. An innovative solution proposed by the authors is to define classes of plug-in hybrid vehicles (classes from A to C) due to exhaust emissions. An innovative way is to determine the extreme results of exhaust gas emission within the range of acceptable scatter of the obtained results. By valuating vehicles, it will be possible in the future to determine the guidelines useful in designing more environmentally friendly power units in plug-in hybrid vehicles.