In biomass gasification processes, the formation and handling of tars are of major concern. Robust and versatile analytical tools are needed to on-line monitor tar compound concentrations in process gases from lab- to industrial scale. This study addresses the development and application of an on-line UV–Vis method, based on a liquid quench sampling system. The high sensitivity of this method allows to detect UV–Vis active tar compounds in the low ppmv region. Recorded spectra from the liquid phase were analyzed for their tar composition by means of a classical least squares (CLS) and partial least squares (PLS) approach. The developed method was applied to two case studies, involving a lab-scale tar reformer and a pilot-scale gas scrubber. Quantification results in gases with limited complexity in tar composition showed good agreement with off-line reference methods (GC-FID). The case studies show that the developed method is a rapid, sensitive tool that can be applied for qualitative process monitoring with the added benefit of quantification in gases with a limited number of tar compounds.