An　environmentally　friendly　and　efficient　electrochemical　fluoroselenation　reaction　of　olefins　has　been　developed.　With　the　use　of　commercially　available　diaryl　diselenides,　triethylamine　trihydrofluoride,　and　olefins,　a　diverse　array　of　β-fluoroselenides　could　be　readily　obtained.　The　reaction　conditions　are　mild,　tolerating　a　wide　range　of　substrates　in　excellent　yields　and　selectivity,　and　can　be　easily　extended　to　gram-scale　preparation　of　vicinal　fluoroselenides,　too.　©　2022　Wiley-VCH　GmbH.