Miscellaneous pesticides and related compounds comprise substances that can neither be included in the classical chemical category of pesticides nor classified by their mode of action. They are a heterogeneous group of substances, the most representative of which are macrocyclic lactones, chloronicotinyls, tetranortriterpenoids, ammonium quaternary salts, dinitroanilines, acetamides, oximes, triazoles, and pyridine‐based molecules. The pesticides covered in this article have hardly changed in the last years. However, their analytical determination has undergone significant improvements. This article provides a well‐defined and critical compilation of the sample treatment and clean‐up procedures, as well as determination techniques applied to miscellaneous pesticides. The new approaches in sample preparation in environmental matrices, such as air, water, soil, food and biological samples, are described. Analytical techniques for characterizing these compounds, which mostly include gas chromatography (GC) and high‐performance liquid chromatography (HPLC) coupled to mass spectrometry (MS), are discussed. Both techniques have almost completely displaced other chromatographic methods. However, in the frontier between chemical and biological techniques, the development of biosensor techniques is very promising. Here, analytical methods applied to the field of real samples are also presented.