The study of the possibilities of supercritical fluid extraction (SFE) with N-nitrosamines in rubbers has been carried out. Home-made materials fortified with several N-nitrosamines were prepared in order to optimize the SFE parameters. A Plackett-Burman design was employed to evaluate the influence of those parameters to be controlled in SFE, such as pressure, temperature, static and dynamic time, restrictor temperature and volume of modifier while CO2 was used as the extraction fluid. An extra central composite design for the main factors (according to the previously obtained results) was also developed in order to refine the best supercritical conditions for the extraction of N-nitrosamines from rubbers. Gas chromatography with a nitrogen and phosphorus sensitive detector was used to achieve sensitivity and limits of detection for the concentrations expected in plastic materials. The proposed analytical method has shown to be useful in the determination of N-nitrosamines even for complex matrices.