Stereoselective [1 + 1 + 4 + 4] dimerization of 1-styrylnaphthols has been developed by using Selectfluor as the oxidant for the first time. The reaction was compatible with various functional groups, giving a class of ethanodinaphtho[b,f][1,5]dioxocines with novel 3D skeletons. DFT calculations indicate that this method merges an intriguing stereoselective intermolecular 1 + 1 radical coupling to construct a bridged C-C bond and then an intramolecular [4 + 4] formal cycloaddition of the in situ generated o-quinone methide intermediate.