New analytical functionality is demonstrated with an enclosed interface that joins a solid phase microextraction (SPME) device, a direct analysis in real time (DART) probe, and a high-resolution mass spectrometer. With a single 20 mm long SPME Arrow, the interface is able to perform five discrete DART analyses on different areas of the same fiber in 1 min of practical operation time. Three-fiber replicates for 15 runs total produce 15% or better center of variance (CV) values for both volatile headspace sampling and direct immersion sampling of a solvated analyte. Chemometric analysis of rapidly acquired headspace data is able to distinguish volatile profiles. Selective desorption within the interface also confers the ability to selectively sample to discrete areas of a fiber, and three different headspace samples or five different liquid samples can be acquired and differentiated with one Arrow. A five-point standard addition curve is constructed to measure the concentration of the solvated analyte. Unmodified commercial components of the analysis system include the fiber itself, the Orbitrap and AccuTOF mass spectrometer platforms, and the conditioning gas chromatograph inlet. Machine diagrams for the SPME-DART interface and Arrow fiber holder are included.