GCxGC-MS is the ideal analytical technique to accommodate the complexity of the samples due to its enhanced peak capacity and sensitivity. For quantitative purposes, and when using flow modulation, splitting to a FID is a logical choice. Sample preparation and sample introduction introduce further challenges due to the complex nature of the samples. Headspace-SPME Arrow is a fully automated sample preparation technique with the ability to extract targeted key compounds present a low concentrations whilst avoiding matrix compounds present at high concentrations. The combination of HSSPME Arrow with GCxGC-MSD/FID is a very powerful tool in the comparative analysis of samples with complex matrices.