Miscellaneous pesticides and related compounds include the compounds that can neither be included in the classical chemical category of pesticides nor classified by their class of action. They are a heterogeneous group of substances like macrocyclic lactones, chloronicotinyls, tetranortriterpenoids, ammonium quaternary salts, dinitroanilines, acetamides, oximes, triazoles and pyridine‐based molecules. Their common characteristic is that they are recently developed pesticides. Sample preparations in environmental matrices: air, water, soil, food and biological samples are described. Analytical techniques for characterizing these compounds include gas chromatography (GC), high‐performance liquid chromatography (HPLC), and a wide variety of other emerging techniques such as capillary electrophoresis (CE), supercritical fluid chromatography (SFC), voltammetric and immunoassay techniques. Here, those applied to the field of real samples are presented.