Pentaerythritol derivatives containing four mesogenic groups with chiral moieties were synthesized. Cholesterol and 2-methyl-1-butanol were used as a chiral moiety. All compounds which derivate from pentaerythritol and mesogenic group showed a glass transition temperature above room temperature, Crystallization from melt of these compounds was strongly suppressed. The compound that the mesogenic group has one benzene ring linked by ester bonding between mesogenic and cholesteryl group exhibited the smectic A(1) phase. While the compounds that the mesogenic group has two benzene rings linked by ester bonding with cholesteryl group exhibited the cholesteric phase. The compounds that the mesogenic group has three benzene rings linked by one ester bonding with 2-methlbutyl group also exhibited the smectic A(2) phase and the cholesteric phase.