Abstract Green analytical chemistry concept, involving the development of analytical methodologies with an environmental concern, encourages the use of direct analysis to avoid any sample treatment that involves energy and reagent consumption and generation of wastes. However, the determination of target analytes at trace concentration levels or in complex matrices frequently requires previous extraction, pre-concentration, or clean-up steps offering thus, additional possibilities for greening classical methods. So, a green evaluation of alternative extraction techniques to currently used ones for the extraction of solid, liquid, and gaseous samples has been carried out in this study. Moreover, the incidence of the continuous increase of laboratory plastic ware consumption, employed for sample treatment, has been highlighted and discussed as a new challenge to enhance the sustainability of analytical methods.