Atomic fluorescence spectrometry (AFS) is a highly sensitive, highly selective technique for analysis of some elements, and it has found extensive applications in environmental analysis. This article presents an overview of the theoretical principles and instrumentation design of atomic fluorescence, followed by demonstrations of AFS, stand alone or coupled with other instruments, application in environmental analysis. For analysis of mercury, for which cold vapor generation can be simply and efficiently used as atomization method, and hydride‐forming elements (e.g. arsenic and selenium), for which gaseous hydrides can be easily produced and volatilized, facilitating the separation and enrichment of the analytes, AFS is a particularly useful technique, including speciation analysis of these elements by coupling AFS detection to chromatography separation.