In the last decade, the development and adoption of greener and sustainable microextraction techniques have been proved to be an effective alternative to classical sample preparation procedures. In this review, 10 commercially available solid-phase microextraction systems are presented, with special attention to the appraisal of their analytical, bioanalytical, and environmental engineering. This review provides an overview of the challenges and achievements in the application of fully automated miniaturized sample preparation methods in analytical laboratories. Both theoretical and practical aspects of these environment-friendly preparation approaches are discussed. The application of chemometrics in method development is also discussed. We are convinced that green analytical chemistry will be really useful in the years ahead. The application of cheap, fast, automated, “clever”, and environmentally safe procedures to environmental, clinical, and food analysis will improve significantly the quality of the analytical data.