We propose a new approach to the phosphorylation of benzenes bearing both electron withdrawing and electron donating substituents on the ring and some coumarins (coumarin, 6-methylcoumarin, 7-methylcoumarin) under the action of dialkyl H-phosphonate (RO)(2)P(O)H (R= Et, n-Bu, i-Pr), based on catalytic oxidation of arene and H-phosphonate (1:1) mixture in electrochemically mild conditions (room temperature, normal pressure) using the bimetallic catalyst system Mn(II)bpy/Ni(II)bpy (1%). This method produces a dialkyl aryl phosphate with high yield (up to 70%) and 100% conversion of H-phosphonate. (C) 2016 Elsevier B.V. All rights reserved.