Two series of hydrogen-bonded liquid crystal complexes have been obtained from binary mixtures of 4, 4′-bipyridine and 2-fluoro-6-X-4-alkoxybenzoic acids (where X = H or F) with a molar ratio of 2:1. The fluorinated proton donors were synthesized firstly and then their chemical structures measured by EA, FTIR, 1H NMR and 13C NMR. The existences of hydrogen bonds between the proton donors and acceptors were identified by FTIR. The liquid crystalline properties of these complexes were investigated by differential scanning calorimeter (DSC), polarizing optical microscopy (POM), and X-ray diffraction (XRD). The results indicated that these complexes with different alkoxy chains and numbers of lateral fluorine atoms exhibited different phase properties. Especially, when the alkoxy chains were short enough, the mesophase of the complexes disappeared.