In this article, a detailed overview of the current high‐performance liquid chromatography/mass spectrometry (HPLC/MS) instrumentation, suitable for the determination of a large number of pesticides, is reported. Particular emphasis is given to the role of the mass spectrometric apparatus involved in each interfacing technique with several information regarding the ionization processes, analyzer principles, and system configurations. The article is an up‐to‐date picture of the current instrumentation available and the reader will find only brief references to some important historical approaches that are no longer in use.