An off-line supercritical fluid extraction method has been developed for the determination of polychlorinated biphenyls and organochlorine pesticides at the part-per-trillion level in marine sediments. Four different extraction conditions were evaluated: pure carbon dioxide at 60 °C/220 atm and 100 °C/350 atm; addition of methanol prior to the static extraction at 80 °C/350 atm; addition of methanol prior to the static extraction step and continuously during the dynamic extraction step at 80 °C/350 atm. Only the latter condition gave extraction recoveries that were comparable and for some compounds higher than Soxhlet recoveries. The significance of differences between the two extraction methodes was determined in an F- and t-test. The method was validated by analysis of a reference material from an international intercomparison exercise.