Solid-phase microextraction (SPME) has been applied to the residual solvents determination in pharmaceutical products and was compared with the static headspace. Three fibers with different polymer films were compared and the polydimethylsiloxane/divinylbenzene coated fiber was found to be the most sensitive for the analyzed analytes. Between the investigated sample preparation techniques, gastight-SPME proved to be the most sensitive, with DL values ranging from 5 pg ml(-1) to 2 ng ml(-1). Headspace SPME is more precise, with RSD of peak areas values ranging from 2 to 3%. The headspace SPME method was successfully validated. The validation data are reported in the text. The most important difference between the two techniques is that the gastight SPME showed better behavior towards very volatile solvents. Compared with the static headspace technique, both SPME methods showed superior results, being compatible with the pharmaceutical samples.