Vehicle interior air quality is an issue of growing interest among car manufacturers and customers. GC-MS is the benchmark method for the analysis of indoor air or material emissions. It is suitable for the quantification of target pollutants and the most abundant compounds. It fails, however, to uncover the true molecular complexity of these samples. In the present study, we describe the development of a TD-GC × GC-TOFMS method designed to detect polar and potentially odorous molecules in car material emissions. Attention is paid to the hyphenation of the thermodesorber and the gas chromatograph, both at software and hardware levels, and the constraints due to pressure limitations on the thermodesorber (evaluated at 414 kPa/60 psi at the end of the temperature ramp and at 138 kPa/20 psi at rest). A compromise was made for the 2D column length and diameter to balance separation and pressure (50 × 0.18 × 0.18 cm × mm × µm + 60 cm transfer line selected). On various materials, we were able to observe several hundreds of polar molecules, among them were between 75 and 150 odorants per material. This work lays the foundation for the widespread screening of potential odorants in car material emissions.