Microalgae play a key role in ecosystems and are widely used in ecological status assessment. Research focusing on such organisms is then well developed and essential. Anyway, approaches for a better comprehension of their metabolome's response towards anthropogenic stressors are only emerging. This review presents the biochemical responses of various microalgae species towards several contaminants including metals and chemicals as pesticides or industrial compounds. We aim to provide a comprehensive and up-to-date overview of analytical approaches deciphering anthropogenic contaminants impact on microalgae metabolome dynamics, in order to bring out relevant biochemical markers that could be used for risk assessment. Studies to date on ecotoxicological metabolomics on microalgae are highly heterogeneous in both analytical techniques and resulting metabolite identification. There is a real need for studies using complementary approaches to determine biomarkers usable for ecological risk assessment.