AbstractBase induced activation of β‐naphthol toward the electrophilic aromatic substitution has been used for the synthesis of the unprecedented 1,1’‐diselanediylbis(naphthalen‐2‐ol) fully characterized by means of NMR and X‐Ray analysis. Its reactivity was studied and the synthesis of novel chiral selenium containing heterocycles was discovered. Chiroptical methods (VCD and ECD) were successfully used to define their absolute configuration and these results represent the first example reported for organoselenium derivatives.