Mass spectrometry (MS) with soft ionisation (i.e. non-fragmenting ionisation) such as photo ionisation (PI) methods are particularly well suited for fast online tobacco analysis. In the past few years several important technical milestones have been set which allow the highly-sophisticated instruments to be operated in common tobacco R&D labs. In cooperation with Borgwaldt-KC GmbH, Hamburg, Germany, a user-friendly prototype system (LM2-Photon-TOFMS) was designed, which is equipped with an ultra compact time-of-flight mass spectrometry system (TOFWERK AG, Thun, Switzerland) and a novel vacuum-ultraviolet (VUV)-lamp system (Coherent, Germany). 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. The photon cross sections of more than 50 tobacco and tobacco smoke with suspected hazards to health were determined for two different wavelengths of VUV-light sources (Ar- (9.8 eV) and KrEBEL (8.3 eV). Application of cross section based quantification was demonstrated on a set of research cigarettes casing the Borgwaldt LM2X-Photon-TOFMS.