Herein, a tandem synthetic route for constructing sulfonyl indanes and dioxadibenzofused macrocycles is described. This strategy involves a transition-metal-free, base-mediated tandem C- and O-alkylative annulation of β-ketosulfones with 1,2-bisbromomethyl arenes with moderate to excellent yields under open-vessel reaction conditions. In the overall reaction process, two carbon–carbon (C–C) and two carbon–oxygen (C–O) bonds are formed. Various base-promoted reaction conditions are screened for this one-pot easy-to-operate conversion.