The main objective of this contribution is to describe the fundamental concepts associated with solid-phase microextraction (SPME). Theory provides insight when developing SPME methods and identifies parameters for rigorous control and optimization. A mathematical model has been developed to understand the principal processes of SPME by applying basic fundamental principles of thermodynamics and diffusion theory. The model assumes idealized conditions and is limited to air, liquid, or headspace above liquid sampling. Theory for ideal cases can be quite accurate for trace concentrations in simple matrices such as air or drinking water at ambient conditions when secondary factors such as thermal expansion of polymers and changes in diffusion coefficients because of solutes in polymers can be neglected. When conditions are more complex, theory for ideal cases still efficiently estimates general relationships between parameters.