The interdependent link between structure and physico-chemical properties of geosorbents and sorption activity of hydrophobic organic pollutants (HOC) upon interaction with solid matrices has been established. The conclusions derived from these investigations have not been actively incorporated into risk assessment and remediation protocols since legislators prefer to adopt a conservative approach when the potential of contaminants to be released from soil matrices are evaluated. With the advent of spectroscopic techniques, it is possible to determine the molecular properties of the geosorbent organic matter which play a pivotal role in HOC retention. Physical-chemical and biological methods are employed to predict the potential for HOC release from sorbent matrices. This article serves as a review discussing the literature and reports the progress that has been made in these particular areas. The implication of employing molecular descriptor factors correlated with a biomimetic method to assess availability and risk is also considered.