Anodic oxidation of triphenylantimony in the presence of various oxygen nucleophiles or halide ions provided the corresponding hypervalent compounds having Sb-Y bonds (Y = RCOO, F, Cl, Br) in good yields. On the contrary, anodic oxidation of triphenylbismuth gave only carbon-bismuth bond cleavage products. Cathodic reduction of anodically synthesized hypervalent organoantimony compounds was also investigated by cyclic voltammetry.