A novel analytical system for gas-chromatographic investigation of complex samples has been developed, that combines the advantages of several analytical principles to enhance the analytical information. Decomposition of high molecular weight structures is achieved by pyrolysis and a high separation capacity due to the chromatographic step provides both an universal as well as a selective and sensitive substance detection. The latter is achieved by simultaneously applying electron ionization quadrupole mass spectrometry (EI-QMS) for structural elucidation and [1+1]-resonance-enhanced-multi-photon ionization (REMPI) combined with time-of-flight mass spectrometry (ToFMS). The system has been evaluated and tested with polycyclic aromatic hydrocarbon (PAH) standards. It was applied to crude oil samples for the first time. In such highly complex samples several thousands of compounds are present and the identification especially of low concentrated chemical species such as PAH or their polycyclic aromatic sulfur containing heterocyclic (PASH) derivatives is often difficult. Detection of unalkylated and alkylated PAH together with PASH is considerably enhanced by REMPI-ToFMS, at times revealing aromatic structures which are not observable by EI-QMS due to their low abundance. On the other hand, the databased structure proposals of the EI-QMS analysis are needed to confirm structural information and isomers distinction. The technique allows a complex structure analysis as well as selective assessment of aromatic substances in one measurement. Information about the content of sulfur containing compounds plays a significant role for the increase of efficiency in the processing of petroleum.