Octanol-water partitioning (Kow) is considered a key parameter for hydrophobicity and is often applied in the prediction of the environmental fate and exposure of neutral organic compounds. However, surfactants can create difficulties in the determination of Kow because of emulsification of both water and octanol phases. Moreover, not only is sorption behavior of ionic surfactants related to hydrophobicity, but also other interactions are relevant in sorption processes. A different approach to develop parameters that can be applied in predictive modeling of the fate of surfactants in the environment is therefore required. Distribution between solid-phase microextraction (SPME) fibers and water was used in this study to measure the affinity of surfactants to a hydrophobic phase. Fiber-water sorption coefficients of alcohol ethoxylates, alkyl carboxylates, alkyl sulfates, and alkyl sulfonates were determined at pH 7 by equilibration of the test analytes between fiber and water. Distribution between fiber and water of anionic compounds with pKa ∼ 5 (i.e., alkyl carboxylates) was dominated by the neutral fraction. Anionic surfactants with pKa ≤ 2 (i.e., alkyl sulfates and alkyl sulfonates) showed strong nonlinear distribution to the fiber. The fiber-water sorption coefficients for alcohol ethoxylates and alkyl sulfates showed a linear trend with bioconcentration factors from the literature. Fiber-water sorption coefficients are promising as a parameter to study the effects of hydrophobicity and other potential interactions on sorption behavior of neutral and anionic surfactants.