Monosubstituted ferrocene based azobenzene liquid crystals were synthesized, in which ferrocene was flexibly attached to the mesomorphic core by click reaction. The counterpart compounds without ferrocene unit were also prepared. Two series of compounds displayed liquid crystal behaviours during heating and cooling, and had wide mesophase range. In the process of cooling, the compounds underwent a transformation from nematic phase to smectic C phase. When ferrocene was introduced into the molecule, the melting point of most compounds decreased by 30–40 °C, and the mesophase range was still as wide as 71–97 °C. These compounds emitted fluorescence at 400–550 nm and had strong absorption near 280 nm and 350 nm. Under the irradiation of 365 nm ultraviolet light, these compounds transformed rapidly from E to Z isomers, while the reverse reaction occurred slowly in the dark, especially the molecules containing ferrocene. Cyclic voltammetry studies showed that ferrocene based azobenzene derivatives exhibited one electron transfer processes with low formal redox potentials, indicating that these compounds are easily oxidized.