A novel enantioselective photochemical pinacolization utilizing the interlayer spaces of layered double hydroxide (LDH) was investigated. UV irradiation of (+)-4-(alpha-hydroxy-alpha-phenyl)-methylbenzoate [benzhydrol-4-carboxylate] ions (d-BHA) with 4-benzoylbenzoate ions (BBA) gave rise to the formation of (-)-1,2-bis(4-carboxyphenyl)-1,2-bisphenyl-1,2-ethanedioI (l-benzopinacol) in the LDH interlayers. Similarly, l-BHA reacts with BBA to give d-benzopinacol in the LDH. A maximum optical yield of over 60%ee was observed at the initial reaction stage.