A novel and convenient protocol for the synthesis of hexahydroxy [2.1.2.1.2.1]- and octahydroxy [2.1.2.1.2.1.2.1] metacyclophanes from 4-substituted phenol in four steps has been developed. The synthetic route involved the preparation of the key intermediate 1,2-bis(5-substituted-2-hydroxyphenyl) ethanes in good yields via (i) formylation of 4-substituted phenol, (ii) reductive deoxygenation of 5-substituted 2-hydroxy aromatic aldehydes with low-valent titanium reagent and (iii) catalytic hydrogenation. The metacyclophanes were prepared by base-catalyzed macrocyclization of the above intermediates with formaldehyde in refluxing xylene in high yields.