A modified Solid-Phase Microextraction (SPME) device has been used as a passive sampler to determine the time-weighted average (TWA) concentration of volatile organic compounds (VOCs) in air. Unlike conventional sampling with SPME, in which the fiber is extended outside its needle housing, during TWA passive sampling, the fiber is retracted a known distance into its needle housing. The SPME passive sampler collects the VOCs by the mechanism of molecular diffusion and sorption on to a coated fiber as collection medium. This process has been shown to be described by Fick's first law of diffusion, whereby determination of the amounts of analytes accumulated over time enable measurement of the TWA concentration to which the sampler was exposed. A series of fibers, 100-microm poly(dimethylsiloxane), 65-microm poly(dimethylsiloxane)/divinylbenzene, and 75-microm Carboxen/poly(dimethylsiloxane), were tested for their "zero sink", face velocity, and response time behavior. Of the fibers tested, that coated with 75-microm Carboxen/poly(dimethylsiloxane) was found to be an excellent passive sampler for VOCs. TWA passive sampling with a SPME device was shown to be almost independent of face velocity and to be more tolerant of high and low analyte concentrations and long and short sampling times, because of the ease with which the diffusion path length could be changed. It was found that environmental conditions, e.g., temperature, pressure, relative humidity, and ozone, have little or no effect on sampling. The 75-microm Carboxen/poly(dimethylsiloxane) fiber can retain VOCs for up to two weeks without significant loss. When the SPME device was tested in the field and the results were compared with those from National Institute of Occupational Health and Safety method 1501, good agreement was obtained.