In the current discussion about future energy and fuel supply based on regenerative energy sources, the so-called second-generation biofuels represent a vitally important contribution for the provision of carbon-based fuels. In this framework, at the Karlsruhe Institute of Technology (KIT), the bioliq process has been developed, by which biomass is flash-pyrolyzed at 500 degrees C for the production of so-called biosyncrude, a suspension of the pyrolysis liquids and the remaining biochar. However, little is known about the composition of the pyrolysis gases in this process with regard to different biomass feedstock and process conditions, and the influence on the subsequent steps, namely, the gasification and subsequent production of biofuels or base materials. Time-of-flight mass spectrometry (TOFMS) with two soft (i.e., fragmentation free) photoionization techniques was for the first time applied for on-line monitoring of the signature organic compounds in highly complex pyrolysis gases at a technical pyrolysis pilot plant at the KIT. Resonance-enhanced multiphoton ionization with TOFMS using UV laser pulses was used for selective and sensitive detection of aromatic species. Furthermore, single-photon ionization using VUV light supplied by an electron beam-pumped excimer light source was used to comprehensively ionize (nearly) all organic molecules. For the miscellaneous biomass feeds used, distinguishable mass spectra with specific patterns could be obtained, mainly exhibiting typical pyrolytic decomposition products of (hemi)cellulose and lignin (phenol derivatives), and nitrogen-containing compounds in some cases. Certain biomasses are differentiated by their ratios of specific groups of phenolic decomposition products. Therefore, principal component and cluster analysis describes the varied pyrolysis gas composition for temperature variations and particularly for different biomass species. The results can be integrated in the optimization of the bioliq process.