Over the years, the topic of microextractive methods capable of generating high recovery values of analytes even from very complex matrices has received increasing attention. Techniques such as dispersive liquid-liquid microextraction (DLLME), microextraction by packed sorbent (MEPS), liquid-liquid extraction (LLE), solid phase microextraction (SPME), solid phase extraction (SPE), fabric phase sorptive extraction (FPSE), and molecular imprinted polymers (MIPs) are certainly the most widespread. These techniques have been widely applied in many fields including bioanalysis, the environment, food, natural compounds, forensic science, and toxicology. This chapter examines recent applications of these novel procedures, highlighting the main benefits and outcomes that have been reported in the literature. Special attention is focused on green approaches and the development of innovative procedures that have been optimised in agreement with green analytical chemistry (GAC) principles. © 2024 John Wiley & Sons Ltd.