In the past few years application of modern analytical techniques, such as time-of-flight mass spectrometry (TOF-MS) with soft ionisation methods have revealed many interesting aspects in complex dynamic matrices, such as tobacco smoke. Unlike the well established off-line techniques (GC, HPLC) there is no need for time consuming trapping, solvent extraction or derivatisation as the composition of multi-component mixtures can be analyzed directly within microseconds. The application of single-photon-ionization (SPI) on various working fields within tobacco research was demonstrated within the past few years. The invention of new sources for intense VUV light especially became of interest for photo ionization techniques, such as SPI and provides a useful tool for the construction of rugged instruments, such as the Borgwaldt LM2X-Photon-TOFMS. In principle, the use of photons proves very useful in terms of quantification as each component inhibits distinctive interactions with photons of specific wavelengths. In a mixture of various different compounds quantification is possible knowing only one exact concentration and the specific relative cross sections of the other compounds to this substance. In this study cross sections of more than 50 compounds with suspected hazards to health were determined for two different wavelengths of VUV-light sources (Ar- and Kr-EBEL) and application was demonstrated on a set of 2R4F research cigarettes using the Borgwaldt LM2X-Photo-TOFMS.