There has been and continues to be considerable scientific interest in predicting bioremediation rates and endpoints. This requires the development of chemical techniques capable of reliably predicting the bioavailability of organic compounds to catabolically active soil microbes. A major issue in understanding the link between chemical extraction and bioavailability is the problem of definition; there are numerous definitions, of varying degrees of complexity and relevance, to the interaction between organic contaminants and microorganisms in soil. The aim of this review is to consider the bioavailability as a descriptor for the rate and extent of biodegradation and, in an applied sense, bioremediation of organic contaminants in soil. To address this, the review will (i) consider and clarify the numerous definitions of bioavailability and discuss the usefulness of the term 'bioaccessibility'; (ii) relate definition to the microbiological and chemical measurement of organic contaminants' bioavailability in soil, and (iii) explore the mechanisms employed by soil microorganisms to attack organic contaminants in soil.