β-CD was reacted with 1, 3-propane sultone in NaOH solution to afford sulfopropyl ether β-cyclodextrin, and subsequently, it was further treated with acidic resin to give β-cyclodextrin-propyl sulfonic acid (β-CD-PSA). In order to optimize the conditions, the condensation reaction of benzaldehyde and β-naphthol was examined in presence of different amounts of β-CD-PSA under various reaction conditions. A series of 14-alkyl- or aryl-14H-dibenzo[a,j]xanthenes were synthesized in presence of 1 mol% of β-CD-PSA, in water at 100 ℃ to afford the corresponding compounds in 85~95% within 6~60 min. The catalyst can be reusable. It could be reused ten-times without a significant loss of catalytic activity. The present protocol offers several advantages, including simple work-up procedure, high yields, short reaction time and benignity procedure.