A simultaneous thermogravimetry/differential scanning calorimetry device (STA) was coupled to single photon ionization time of flight mass spectrometry (SPI-TOFMS) for evolved gas analysis (EGA). Thermal resolution with thermogravimetric signals (TG/DTG) is delivered by STA. On-line coupled EGA with SPI-TOFMS retains the thermal information from the STA and substantiates these with correlating mass spectra. The application of vacuum ultraviolet (VUV)-photons (8-12 eV) for soft ionization, allows almost fragment-free ionization. Thus, it becomes possible to interpret mass spectra of complex matrices, like natural products evolving simultaneously several molecules, without an additional separation step. The STA-SPI-TOFMS on-line coupling offers the possibility to track subset mass traces during one STA run. Focusing on material-depended mass traces, differentiation of organic matrices is obvious. In this work two types of research cigarettes, 3R4F and CM6 were used. While the 3R4F cigarette is composed of a blend of different tobacco sorts and different curing methods, the CM6 research cigarette consists of pure flue cured tobacco. The advantages of coupling on-line chemical analysis methods to thermal analysis (TA) are in the context of the achieved thermo-molecular signatures.