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Covering: up to 2015 Over the last decade, the number of studies reporting the use of electrospray ionization mass spectrometry (ESI-MS) in combination with collision cells (or other activation methods) to promote fragmentation of synthetic and natural products for structural elucidation purposes has considerably increased. However, the lack of a systematic compilation of the gas-phase fragmentation reactions subjected to ESI-MS/MS conditions still represents a challenge and has led to many misunderstood results in the literature. This review article exploits the most common fragmentation reactions for ions generated by ESI in positive and negative modes using collision cells in an effort to stimulate the use of this technique by non-specialists, undergraduate students and researchers in related areas.