Electrochemical synthesis of dicoumarols as anticoagulant drugs was carried out by the electrochemical oxidation of N,N,N′,N′-tetramethyl-1,4-phenylenediamine in the presence of 4-hydroxycoumarin derivatives. Electrochemically generated radical cation participates in cross-dehydrogenative coupling (CDC) reaction with 4-hydroxycoumarins. The present work has led to the development of a facile catalyst-less, one-pot and environmentally friendly method under ambient conditions using a carbon electrode.