Two series of novel trimers with benzylidene-1,4-phenylenediamine core units attached by two (S)-2-methylbutyl 4-(4'-phenyl)benzoate moieties via methylene groups at terminal ends have been synthesized and characterized. In each series, the title compounds differ from each other in term of spacers -OCnH2nO- wherein n ranges from 5 to 12. The difference of the second series from their analogues in the first series is due to the presence of two OCH3 groups residing at the meta position in the benzylidene-1,4-phenylenediamine mesogenic core. The trimers without lateral OCH3 groups exhibit the SmC* and SmA phases in addition to the N* phase suggesting the possession of high molecular shape anisotropy. The higher-order tilted smectic phases and the blue phase are also observed for the members with odd n numbers in the first series. In the second series, however, the smectogenic characteristics are absent. Whilst the even-parity trimers are nematogenic, the trimers with odd spacers are not mesogenic. The trimers without lateral OCH3 groups in the first series also exhibit higher mesophase thermal stability in comparison with their analogues in the second series.