In last three decades, the solid-phase microextraction technology has brought significant progress in bioanalytical research due to the versatility of this fast and solvent-free approach to biological sample preparation. It has been widely used in combination with various analytical instrumentation, even if most of the work has been done by coupling the extraction technique with liquid or gas chromatography. This review focuses on the new developments and advances in solid-phase microextraction-based techniques. Furthermore, some interesting, new innovations that fail to go beyond academic research are also reported.