The determination of organic trace gases in the ambient environment at the lower ppb level is demonstrated based on a novel technique combining sorption tube sampling on Molsieve and Carbosieve S-III, thermal desorption, and detection of the trace analyte by hollow waveguide Fourier transform infrared (HWG-FT-IR) spectroscopy. While ethene concentrations of ∼5 ppm can be directly observed using HWG-FT-IR, enrichment factors of up to 5000 were achieved by sorption tube sampling and thermal desorption. Detection limits of ∼1 ppb are reported. Efficient enrichment by the sampling tube is achieved due to the favorable internal volume (∼0.4 cm3 at a length of 470 mm) of the hollow waveguide serving as a miniaturized gas cell. This new method was validated for ethene by thermodesorption-cryofocusing-GC-FID as the reference method. Analytical performance has been compared for standard gas mixtures and for ethene measurements in urban air. Finally, ethene data from a sampling campaign at two alpine sites in Tyrol/Austria are presented.