The synthesis, characterization and mesogenic properties of a new family of 1,3-disubstituted ferrocene derivatives and of the first trisubstituted ferrocene-containing thermotropic liquid crystals (here functionalized in the 1,1′,3-positions) are reported. The results confirmed the importance of the organic segment length for promoting mesomorphism in disubstituted systems and revealed the strong tendency of polysubstitution for generating liquid-crystalline materials.