Stir bar sorptive extraction (SBSE) is sample preparation technique that involves the extraction and enrichment of organic compounds from a liquid sample. The technique is based on the principle of sorptive extraction. A large amount of extraction phase is coated on a stir bar. An analyte is extracted into the extraction phase, based on its octanol-water partitioning coefficient and the phase ratio. Recently, various methods involving SBSE were developed in order to further facilitate analysis and improve sensitivity. In this review, we focused on the novel methods that involve SBSE with in situ derivatization, SBSE with in situ de-conjugation, thermal desorption (TD) in the multi-shot mode and TD with in tube derivatization method. Those methods were applied successfully to the trace analysis of environmental and biological samples and extremely low detection limits were achieved.