Improvement of sorption based sample preparation techniques and/or the development of new materials for these same techniques are/is extremely important to extend their (its) applicability, efficiency and robustness. The fragility of fused silica and the necessity of robust supports for solid phase microextration (SPME), as well as the importance of an efficient interaction between the extractor coating and the support, have driven the development and application of new materials. In this review the use of metallic wires as a support to “unbreakable” SPME fibers will be discussed. The focus of this paper will be the use of NiTi alloy coated with ZrO2 by eletrodeposition and its evaluation as support and extracting sorvent for SPME, as well as substratum for sol-gel reactions with com polidimetilsiloxano (PDMS) and polietilenoglicol (PEG).