Two new tetracationic ammonium salts based on 1,4‐diazabicyclo[2.2.2]octane (DABCO) were prepared and applied as an environmentally benign, powerful and reusable catalyst for the synthesis of xanthenes and benzoxanthenes via condensation of an active methylene compound, salicylaldehyde and an electron‐rich arene in water. It also efficiently catalyzed synthesis of bis(indolyl)methanes from indoles and aldehydes in water.