A simple and efficient method for the synthesis of functionalized di-aromatic ring-fused 2,8-dioxabicyclo[3.3.1]nonane derivatives catalyzed by silver triflate from easily available 2-hydroxychalcones and naphthols/substituted phenols is described. Two six-membered cycles were formed in a one-pot operation. This reaction was probably achieved via a Friedel–Crafts alkylation/bicyclization domino process.