Biotin-TEG-ATFBA is a click chemistry reagent containing a perfluorophenylazide group. Biotin-TEG-ATFBA forms a highly stable azene intermediate that undergoes insertion and addition reactions (non-intermolecular rearrangement) in moderate to good yields after photolysis. It contains an azide group and can undergo copper-catalyzed azide-alkyne cycloaddition (CuAAc) with molecules containing alkyne groups. It can also undergo ring strain-promoted alkyne-azide cycloaddition (SPAAC) with molecules containing DBCO or BCN groups.