Liquid crystalline 1,1′-disubstituted ferrocene derivatives, 1,1′-bis[ω-[4-(4′-methoxyphenoxycarbonyl)phenoxy]alkoxycarbonyl] ferrocene (abbreviated hereafter to bMAF-n,n= 2∼12, wherenis a carbon number of the methylene chain units), were synthesized, and their phase transition behavior was studied using a differential scanning calorimeter and a polarizing microscope. The liquid crystal structures of the compounds were investigated by the X-ray diffraction method. Nine of eleven compounds of the samples showed liquid crystallinity. The liquid crystalline phases were identified as a nematic (n= 3 and 5∼12), a smectic C (n= 5∼12) and a smectic F or I (n= 11 and 12). As a model structure of the smectic phase, a tilted structure with an expanded substituent is presented.