The thermal properties of two ferrocene derivatives, substituted by either one or two cholesteryloxycarbonyl units, were investigated. While the monosubstituted ferrocene derivative 1 was found to be non‐mesomorphic, the disubstituted ferrocene derivative 2 exhibited a crystal smectic‐B phase. This result shows that ferrocene‐containing thermotropic liquid crystals, despite the bulkiness of the metallocene core, are not limited to disordered calamitic phases.