A new family of phosphorus-based chiral liquid crystals is described. Dibenzophosphole oxides containing an asymmetric center at the phosphorus atom show cholesteric and smectic liquid crystalline behavior. The presence of the chiral center in the rigid heterocyclic core avoids the need for destabilizing chiral aliphatic branched substituents at the mesogenic unit. Racemic mixtures of the synthesized dibenzophospholes exhibit both nematic and smectic phases.