Dodecahydrotriphenylene, a higher homologue of trindane chemoselectively undergoes unidirectional benzylic sp³ C–H oxidation and the central benzene ring remains intact unlike that in trindane under similar reaction conditions. RuO₄ which generally attacks sp² C–H to form oxidative products is found to give benzylic ketones via sp³ C–H oxidation. Density functional theory (DFT) calculations have also been performed to analyse the potential energy, energy barrier and HOMO–LUMO energy gap of the products.