The electrochemical oxidation of bis(organylchalcogeno)acetylenes has been examined in organic solvents. With symmetrical ones, R-Z-C equivalent to C-Z-R (1) (Z = S, Se), and with unsymmetrical ones, R-1-S-C equivalent to C-Z-R-2 (2) (Z = Se), in macroscale electrolyses the alpha-diesters R-1-Z(S)-CO-CO-Z-R-2 were obtained as the main products. If Z = Te, from 1 and 2, reactions were more complex and the cleavage of the C-Te bond was always observed.