HS-SPME-GC-MS in combination with PCA was employed to discriminate different arabica/robusta blends having different geographical origins. HS-SPME confirmed to be an effective and reproducible sampling technique for routine characterization of coffees. In addition, the chemometric approach permitted to find parameters suitable for the differentiation of the different blends and the determination of the real quality of the products. Finally, the proposed methods have been successfully applied to some commercial coffee blends.