An efficient and facile synthesis of biologically active 14-substituted- 14-H-dibenzo[a,j] xanthene derivatives were reported via three-component condensation reaction of P-naphthol and aldehydes in the presence of a catalytic amount of Preyssler type heteropoly acid, under solvent-free conditions. This method is very easy, rapid and high yielding reaction for the synthesis of dibenzo xanthene derivatives. (C) 2007 Elsevier B.V. All rights reserved.