This study aims to examine tire and road wear particle (TRWP) emissions under realistic conditions in order to provide some valuable insights into understanding their sources and fate in the environment. TRWP emissions were evaluated with a fully instrumented vehicle driving on five representative road types: urban, ring road, suburban, highway, and rural. Multiple vehicle dynamic variables were recorded to assess the factors influencing these emissions. For the first time, emitted particles were collected on filters and analyzed by means of pyrolysis coupled with gas chromatography-mass spectrometry to determine the polymeric content of tires, in specifically quantifying styrene-butadiene rubber (SBR) and butadiene rubber (BR) pyrolytic markers. The measurements obtained from the five road types revealed similar size distributions for SBR + BR emissions, with maxima found in the (ultra)fine fraction (< 0.39 µm). Upon applying an SBR + BR-to-TRWP conversion factor, (ultra)fine fraction TRWP emissions proved to be the highest for suburban (64 ± 5 µg/km), followed by highway, urban, ring road and rural routes. The output represents up to 480 tons of TRWP per year emitted in the EU27, thus suggesting a widely impregnated atmospheric compartment capable of threatening human health. Furthermore, an analysis of variables revealed that acceleration, tire constraints, and constant sustained driving factors had specific impacts on TRWP emissions.