Solid phase microextraction (SPME) presents many advantages over conventional analytical methods by combining sampling, pre-concentration and direct transfer of the VOCs into a standard gas chromatography (GC) system. Since its introduction SPME has been applied to the sampling and analysis of environmental samples including airborne VOCs and particulates. The first part of this paper presents theory of air sampling with SPME and an overview of the a few current methods for quantitative air sampling and VOC determination with SPME using grab (‘instantaneous”) and time-weighted average (TWA) modes. The second part of this paper is focused on the recent development of the theory and applications of rapid air sampling and quantification of VOCs in air with adsorptive SPME fiber coating. This approach based on forced and controlled air flow of sampled air and diffusion-based calibration, reduces the effects of VOC competition and displacement. Experiments are currently conducted to apply the rapid SPME sampling method to determination of chemical composition and concentrations of agricultural odors.