A sample introduction system configured for introducing analytes of a solid phase micro extraction (SPME) sample into an analytical instrument system (e.g., mass spectrometer) is described. The sample introduction system includes a pressure vessel configured with an inlet port via which a probe portion (e.g., SPME fiber) of a SPME assembly is received into a sealed volume of the pressure vessel. The probe portion of the SPME assembly is coated with an extracting phase material, the analytes being absorbed into and/or adsorbed onto the extracting phase material. The pressure vessel is configured for providing an environment in which desorption of the analytes from the extracting phase material occurs at a gaseous pressure which is substantially less than atmospheric pressure (e.g., less than 100 mTorr). The desorbed analytes are then directed to the vacuum chamber of the analytical instrument system via an outlet port of the pressure vessel.