The analysis of chemical compounds present at very low concentrations in complex matrices (e.g., residues and contaminants in food samples) usually requires a complex analytical approach, involving sampling, sample preparation, analyte isolation and qualitative and quantitative determination. Most analysts consider sample preparation to be the Achilles' heel, because it is usually time consuming, presents low yields, is prone to introducing contamination, and is more difficult to automate than other steps. Recently, a strong movement towards utilization of greener analytical methods stimulated development of microextraction techniques. Most of these microextraction techniques are based upon sorption processes, making the development of novel sorptive materials one of the most active research areas in this field. In the present work, we present a review on the new materials recently developed for sample preparation in line with the concept of green analytical chemistry. We also review the techniques using them and their main applications.