The analytical application of direct pyrolysis (Py) field ionization (FI)-mass spectrometry (MS) und Curie-point pyrolysis gas chromatography-mass spectrometry (Py-GC/FIMS) to various whole foodstuffs is described for the first time. The former technique yields highly differentiated information from the sample in typically 15 min, namely the molecular weight distribution of released volatiles and pyrolysis products in a single spectrum which, owing to the good reproducibility and high significance of the resulting data, has previously been shown to be suitable for the application of chemometric methods. Such mass spectral peaks are further characterized and assigned by high resolution mass measurement and/or by electron ionization after Curie-point pyrolysis and gas chromatographic separation of the components. In this first report, typical results are presented for ground roasted coffee, rosehip tea, wheatmeal biscuit, chocolate drink powder and milk chocolate. The FI mass spectrum obtained from the latter sample is compared with those obtained using the complementary soft ionization techniques of chemical ionization (CI) and direct chemical ionization (DCI).