A new, rapid air sampling/sample preparation methodology was investigated using adsorptive solid-phase microextraction (SPME) fiber coatings and nonequilibrium conditions for volatile organic compounds (VOCs). This method is the fastest extraction technique for air sampling at typical airborne VOC concentrations. A theoretical model for the extraction was formulated based on the diffusion through the interface between the sampled (bulk) air and the SPME coating. Parameters that affect the extraction process including sampling time, air velocity, air temperature, and relative humidity were investigated with the porous (solid) PDMS/DVB and Carboxen/PDMS coatings. Very short sampling times from 5 s to 1 min were used to minimize the effects of competitive adsorption and to calibrate the extraction process in the initial linear extraction region. The predicted amounts of extracted mass compared well with the measured amounts of target VOCs. Findings presented in this study extend the existing fundamental knowledge related to sampling/sample preparation with SPME, thereby enabling the development of new sampling devices for the rapid sampling of air, headspace, water, and soil.