Tributyltin still remains a major issue for the marine environment and its determination is mandatory by legislation in several countries. As for speciation analysis in general, organotin analysis is a highly complex analysis with a long and laborious sample treatment procedure prone to various errors. It is widely recognized that the contribution of sample treatment to the total calculated uncertainty of a method is much larger than the contribution from the instrumental analysis. Furthermore, in contrary to instrumental analysis, sample treatment is far from being under control. Extraction, derivatization when needed, and preconcentration are usually carried out by exploiting a large variety of reagent combinations and techniques characterized by different efficiency and reproducibility. In this chapter new approaches in sample treatment procedures for organotin speciation that have emerged within the last 5 years are presented schematically and discussed briefly underlining the main advantages and disadvantages of the individual solutions. In the extraction and preconcentration steps the new tendencies are oriented towards the use of reduced-solvent or solvent-free systems, such as accelerated solvent extraction (ASE) or solid phase micro extraction (SPME). Derivatization has seen no significant developments within the last 15 years. The most significant development has probably been achieved in instrumental analysis with the application of isotope dilution techniques in order to trace the transformation/degradation of organotin species during the sample preparation steps. This technique will presumably become the most powerful tool for optimizing and validating extraction methods in the near future.