The analysis of human breath is a very active area of research driven by the vision of a fast, easy, and non-invasive tool for medical diagnoses at the point of care. Millimeter-wave gas spectroscopy (MMWGS) is a novel, well-suited technique for this application as it provides high sensitivity, specificity and selectivity. Most of all, it offers the perspective of compact low-cost systems to be used in doctors’ offices or hospitals. In this work, we demonstrate the analysis of breath samples by MMWGS acquired in a medical environment and evaluate validity, reliability, as well as limitations and perspectives of the method. To this end, we investigated 28 duplicate samples from Chronic Obstructive Lung Disease patients and compared the results to Gas Chromatography-Mass Spectrometry (GC-MS). The quantification of the data was conducted by a calibration-free fit model, which describes the data precisely and delivers absolute quantities. For ethanol, acetone, and acetonitrile, the results agree well with the GC-MS measurements and are as reliable as GC-MS. The duplicate samples deviate from the mean values by only 6 % to 18 %. Detection limits of MMWGS depend strongly on the molecular species. For example, acetonitrile can be traced down to 1.8∙10-12 mol by the MMWGS system, which is comparable to the GC-MS system. We observed correlations of abundances between formaldehyde and acetaldehyde as well as between acetonitrile and acetaldehyde, which demonstrates the potential of MMWGS for breath research.