A simple methodology has been developed for the synthesis of substituted 9H-dibenzo[3,4:6,7]-cyclohepta[1,2-a]naphthalenes from phenylacetaldehydes and ortho-alkynyl benzyl alcohols in the presence of a Lewis acid in moderate to good yields within a short reaction time. Interestingly, the reaction proceeds through a highly regioselective electrophilic addition followed by double Friedel–Crafts reaction to form uncommon dibenzo-fused seven-membered carbocycles.