A sensitive analytical method for the determination six PEs implying a minimal sample manipulation has been developed, applying the DSI technique by means of a TDU coupled to GC–MS. This combination allowed an important increase in sensitivity attained with respect to the classical splitless injection mode, considering that large masses of the analytes can be injected into the GC system. In addition, most of the sample matrix components remained in the microvial, thus not damaging the chromatographic stationary phase or the spectrometer components.