This is a state-of-science review of interrelationships between the sorption/desorption behaviors and chemical structures of natural organic matter (NOM) matrices associated with soils, sediments and aquifer materials. It identifies similarities between these behavior-property interrelationships for natural geosorbents and those for synthetic organic polymers. It then invokes, with appropriate restrictions and modifications, several structure-function relationships that have been developed for synthetic polymers to explain the behavior of NOM matrices with respect to the sorption and desorption of hydrophobic organic contaminants (HOCs). Previous research regarding HOC sorption and desorption by different types of NOM and by synthetic polymers is summarized, and research requirements for further refinement of the NOM-polymer analogy are examined. The discussion focuses on structural and compositional heterogeneities that exist at the particle and aggregate scale, a scale at which homogeneity is commonly, and often improperly, assumed in the development of contaminant fate and transport models.