We describe an efficient one-pot regio- and stereoselective method for synthesizing diverse 1-hydroxy-12H-6,12-methanodibenzo[d,g][1,3]dioxocines and 3-hydroxy-12H-6,12-methanodibenzo[d,g][1,3]dioxocines using ethylenediammonium diacetate (EDDA) or p-toluenesulfonic acid (PTSA) catalyzed reactions between various resorcinols and a number of 2-hydroxychalcones. These reactions involve a catalyst-controlled cascade Michael-type reaction/double cyclization process. Importantly, these reactions provide a rapid synthetic route to the production of biologically interesting complex molecules that are generally prepared using multi-step reactions.