Abstract Matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry allows fast and efficient analysis of complex synthetic polymers which always exhibit varying degrees of polydispersity including molar mass distribution and chemical composition distribution. Most commonly used with a time‐of‐flight (TOF) mass analyzer, MALDI MS is the workhorse in polymer mass spectrometry and can be used to 1) identify homopolymers, 2) determine the endgroups of macromolecules, 3) elucidate polymerization mechanisms, 4) analyze copolymers, 5) determine molecular structures, and 6) determine absolute molar masses of oligomers. This paper gives an overview of the mentioned applications of MALDI MS in polymer analysis.