Abstract A new series of side-chain liquid-crystalline dendrimers (LCDs) by grafting vinyl- terminated phenyl benzoate-based promesogens to a novel polypropyleneimine-derived dendritic polyols are reported. Polarized optical microscopy and X-ray diffraction studies show that both the compounds display a smectic-A (SmA) mesophase. The second- generation dendrimer bearing eight-branched promesogens exhibits a more stable SmA ...