The analysis of tar, mostly characterized as polycyclic aromatic hydrocarbons (PAHs), describes a topic that has been researched for years. An online analysis of tar in the gas stream in particular is needed to characterize the tar conversion or formation in the biomass gasification process. The online analysis in the gas is carried out with ultraviolet-visible (UV-Vis) spectroscopy (190-720 nm). This online analysis is performed with a measuring cell developed by the Fraunhofer Institute for Chemical Technology (ICT). To this day, online tar measurements using UV-Vis spectroscopy have not been carried out in detail. Therefore, PAHs are analyzed as follows. The measurements are split into different steps. The first step to prove the online method is to vaporize single tar substances. These experiments show that a qualitative analysis of PAHs in the gas stream with the used measurement setup is possible. Furthermore, it is shown that the method provides very exact results, so that a differentiation of various PAHs is possible. The next step is to vaporize a PAH mixture. This step consists of vaporizing five pure substances almost simultaneously. The interpretation of the resulting data is made using a chemometric interpretation method, the multivariate curve resolution (MCR). The verification of the calculated results is the main aim of this experiment. It has been shown that the tar mixture can be analyzed qualitatively and quantitatively (in arbitrary units) in detail using the MCR. Finally it is the main goal of this paper to show the first steps in the applicability of the UV-Vis spectroscopy and the measurement setup on online tar analysis in view of characterizing the biomass gasification process. Due to that, the gasification plant (at the laboratory scale), developed and constructed by the Fraunhofer ICT, has been used to vaporize these substances. Using this gasification plant for the experiments enables the usage of the measurement setup also for the spectroscopic analysis of the tar formation during the biomass gasification.