The synthesis and properties of laterally 4-nitrobenzyloxycarbonyl substituted phenyl benzoates are described; these compounds represent the first two-ring mesogens having a phenyl ring in the lateral branch. The lengths of the terminal chains of the core carrying the branch have a great influence, as shown by the phase behaviour of two homologous series. Compounds having long alkyloxy groups exhibit enantiotropic smectic A phases. It should be emphasized that the mesophase thermal stability of these strongly branched derivatives can be higher than that of the laterally unsubstituted parent compound. Connecting two of the new mesogens by means of an aliphatic spacer results in a novel type of twin molecule.