This work describes the first fully direct coupling of solid-phase microextraction (SPME) with mass spectrometry. An inlet system using a septum as the only interface between the ambient and the high-vacuum mass spectrometer was constructed to allow the introduction of the SPME needle directly into the ionization region of a mass spectrometer. The PDMS-coated fiber was then placed and exposed exactly between the two ionization filaments. Uniform heating of the fiber, efficient thermal desorption, and electron ionization of the analytes were achieved. Using this new analytical technique, here termed fiber introduction mass spectrometry (FIMS), we have been able to detect and quantitate several volatile (VOC) and semivolatile (SVOC) organic chemicals (carbon tetrachloride, benzene, toluene, xylenes, gamma-terpinene, diisoamyl ether, chlorobenzene, and many PAHs) and two herbicides (Sylvex and its methyl ether) from aqueous solutions at low-ppb to ppt levels using either SPME headspace or solution extraction. FIMS shows high sensitivity (ng/L), good reproducibility, and accuracy, providing therefore a simple and effective approach to rapid analysis of VOC and SVOC in various matrixes.