Anodic alpha-methoxylation and alpha-acetoxylation of substituted phenyl 2,2,2-trifluoroethyl sulfides and various fluoroalkyl phenyl sulfides were studied from both synthetic and mechanistic aspects. These anodic reactions were greatly affected by both substituent groups at the benzene ring and fluoroalkyl groups. Electron-donating substituents interfered with the reactions significantly. Strong electron-withdrawing perfluoroalkyl groups(C(n)F2n+1:n = 1 - 3) remarkably promoted these anodic substitutions while difluoro- and mono-fluoromethyl groups showed much less substitution.