Gas and liquid chromatography-mass spectrometry (GC-MS, LC-MS) methods for the determination of angiotensin-converting enzyme inhibitors (ACEIs) and their metabolites in biological material have been reviewed. Since 1980s those hyphenated techniques have been applied to quantitate ACE inhibitors and the dynamic increase in the number of relevant publications can be observed in recent years. Although most of the methods available in the literature were analyses of plasma or serum, assays of blood and urine were also included. Additionally, sample pretreatment methods, separation conditions and ionization modes were overviewed. Some information on chemical structures, cis-trans izomerization and stability of compounds in question was also included. Most of the reported methods were successfully applied to the pharmacokinetic studies in humans.