Organic electrosynthesis is expected to be a typical green chemical process.1 On the other hand, organofluorine compounds are key materials applied in daily life because of their versatile utility as functional materials, pharmaceuticals, and agrochemicals. Although organic electrosynthesis has a long history2, electrosynthesis of organofluorine compounds has been unexplored until ca. 30 years ago. With these facts in mind, we have developed electrochemical systems for selective fluorination of organic compounds including macromolecules and molecular conversion of organofluorine compound.3-7 In this talk, we will describe selective anodic fluorination and fluoro-desulfurization of dithioacetals and O,S-acetals having α-electron-withdrawing groups using various poly(HF) salts and solvents. It was found that oxidative elimination of α-proton followed by fluorination and fluorodesulfurization were greatly affected by EWG and/or electrolytic conditions.8,9 References1) Fuchigami, M. Atobe, S. Inagi, Fundamentals and Applications of Organic Electrochemistry: Synthesis, Materials, Devices, Wiley, 2014.2) Fuchigami, Chem. Rec., 21 , 2079 (2021).3) Fuchigami, S. Inagi, Acc. Chem. Res., 53 , 322 (2020).4) Inagi, T. Fuchigami, Chem. Commun. (Feature Article), 47 , 10211 (2011).5) Oyanagi, H. Ishii, S. Inagi, T. Fuchigami, J. Electrochem. Soc. 167 155511 (2020).6) Ito, K. Kondo, H. Ishii, S. Inagi, T. Fuchigami, J. Electrochem. Soc., 168, 065502 (2021).7) Shida, T. Fuchigami, S. Inagi et al., J. Org. Chem., 86, 16128 (2021).8) Yin, S. Inagi, T. Fuchigami, Beilstein J. Org. Chem. , 11 , 85 (2015).9) Yin, S. Inagi, T. Fuchigami, Electrochem. Sci. Adv., in press.